I 1 Physical Methods

BY J. C. TEBBY

The abbreviations PI1, PIII, etc. refer to the co-ordination number of phosphorus, and the compounds in each subsection are usually dealt with in this order. A number of relevant theoretical and inorganic studies are included in this chapter. In the formulae, the letter R represents hydrogen, alkyl, or aryl, X represents electronegative substituents, Ch represents chalcogenides (usually oxygen and sulphur), and Y and 2 are used to indicate groups of a more varied nature.

1 Nuclear Magnetic Resonance Spectroscopy Biological Applications-The application of 31P n.m.r. spectroscopy to the study of living tissue has been reviewed.l There have also been further studies on malignant tumours, cells,3 metaboli~rn,~ blood,6 hearty6 other musclesY7 and liver, lung, brain, and There have been other biochemical studiesyg and

M. K. Battersby and P. B. Garlick, Biomol. Struct. Funct. (Symp.), 1977, 1978, p. 175. 2 K. S. Zaner and R. Damadian, Physiol. Chem. Phys., 1977,9,473; L. R. Maxwell and L. H.

Bennett, ibid., 1978, 10, 59. 3 F. E. Evans, Arch. Biochem. Biophys., 1979,193,63; K. Ugurbil, H. Rottenberg, P. Glynn,

and R. G. Shulman, Proc. Narl. Acad. Sci. USA, 1978,75,2244; R. G. Shulman, G. Navon, S. Ogawa, and T. Yamane, Biomol. Struct. Funcr. (Symp.), 1977, 1978, p. 195; S. M. Cohen, S. Ogawa, H. Rottenberg, and P. Glynn, Nature (London), 1978, 273, 554.

4 S. Ogawa, H. Rottenberg, and T. R. Brown, Proc. Natl. Acad. Sci. USA, 1978,75, 1796; A. Omachi and W. E. Marshall, Biomol. Struct. Funct. (Symp.), 1977, 1978, p. 225; T. Glonek and S. F. Marotta, Horm. Metab. Res., 1978, 10, 420. Y . Arata, Kugaku (Kyoto), 1977, 32, 1002; R. K. Gupta, J. L. Benovic, and Z. B. Rose, J. Biol. Chem., 1978, 253, 6172; J. L. Costa, C. M. Dobson, and K. L. Kirk, FEBS Lett., 1979, 99, 141. D. P. Hollis and R. L. Nunnally, J. Magn. Reson., 1978, 29, 319; P. B. Garlick and P. J. Seeley, Proc. FEBS Meeting, 1978, No. 42, Regul. Mech. Carbohydr. Metab., p. 297; W . E. Jacobus and G. J. Taylor, Biomol. Struct. Funct. (Symp), 1977, 1978, p. 207; D. P. Hollis, R. L. Nunnally, and G. J. Taylor, ibid., p. 217; B. H. Bulkley and R. L. Nunnally, Lab. Inoest., 1978,39, 133; P. R. Cullis and A. J. Verkleij, Biochim. Biophys. Acta, 1978, 513, 11.

7 M. J. Dawson, D. G. Gadian, and D. R. Wilkie, J. Physiol. (London), 1978, 282, 20P; Nature (London), 1978,274, 861 ; K. Yoshizaki, J. Biochem. (Tokyo), 1978,84, 11.

8 A. C. McLaughlin, H. Takeda, and B. Chance, Energy Res. Abstr., 1979, 4, No. 3, Abstr. No. 6731; H. Nishikawa, S. Yamada, and K. Yoshizaki, Proc. Jpn. Acad., Ser. B, 1978,54, 397; C. Grathwohl, G. E. Newman, and P. J. R. Phizackerley, Biochim. Biophys. Actu, 1979,552,509; B. Chance, Y. Nakase, and M. Bond, Proc. Natl. Acad. Sci. USA, 1978,75, 4925

9 D. G. Gorenstein, Jerusalem Symp. Quantum Chem. Biochem., 1978, No. 11. Nucl. Magn. Resonance Spectrosc. Mol. Biol., p. 1 ; N. R. Kallenbach, D. W. Appleby and C. H. Bradley, Nature (London), 1978,272,134; D. Njus, P. A. Sehr, and G. K. Radda, Biochemistry, 1978, 17, 4337.

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248 Organophosphorus Chemistry

those on membranes,l* phospholipids,ll nucleotides,12 sugar phosphates,13 and Escherichia coZi14 have sometimes incorporated 13C n.m.r. spectroscopy. Stereochemical studies of nucleotides, etc.,16 and of phosphatidylcholines l6 have utilized lH n.m.r. Chemical Shifts and Shielding Effects.-Phosphorus-3 1, The measurement of

F.T. n.m.r, spectra of viscous samples may be improved by the use of coaxial capillaries containing deuteriated compounds of appropriate polarity and magnetic susceptibility for 2H locking and magnetic shimming. l7 A method for the determination of phosphorus in organophosphorus compounds by 31P F.T. n.m.r. utilized triphenyl phosphate as the standard and chromium

lo B. De Kruijff and A. M. H. P. Van Den Besselaar, Biochim. Biophys. Acta, 1978, 514, 1 ; J. Seelig, ibid., 1978, 515, 105; P. R. Cullis and A. J. Verkleij, ibid., 1979, 552, 546; P. Palatini, B. De Kruijff, and J. De Gier, Experientia, 1978, 34, 1580; H. D. Pierce, A. M. Unrau, and A. C. Oehlschlager, Can. J. Biochem., 1978, 56, 801 ; J. Seelig, Biochem. SOC. Trans., 1978, 6, 40; A. Stier and S. A. E. Finch, FEBS Lett., 1978, 91, 109.

11 F. J. Castellino, Arch. Biochem. Biophys., 1978,189,465; F. J. Castellino and B. N. Violand, ibid., 1979,193,543 ; P. R. Cullis, P. W. M. Van Dijck, and B. De Kruijff, Biochim. Biophys. Acta, 1978, 513, 21; P. R. Cullis and B. De Kruijff, ibid., 1978, 513, 31; M. Koter, B. De Kruijff, and L. L. M. Van Deenen, ibid., 1978, 514, 255; W. J. Gerritsen and E. J. J. Van Zoelen, ibid., 1979,551,248; P. R. Cullis, P. W. M. Van Dijck, and B. De Kruijff, Biochim. Biophys. Acta, 1978, 513, 21 ; A. M. Goetze and J. H. Richards, Biochemistry, 1978, 17, 1733; P. L. Yeagle, R. B. Martin, and L. Pottenger, ibid., 1978, 17,2707; J. Herzfeld, R. G. Griffin, and R. A. Haberkorn, ibid., 1978, 17, 2711; R. G. Griffin, L. Powers, and P. S. Pershan, ibid., 1978, 17, 2718. S. Uesugi and M. Ikehara, Chem. Pharm. Bull., 1978,26, 3040; S . Uesugi, S. Tanaka, and M. Ikehara, Eur. J. Biochem., 1978,90,205; T. Kagimoto, F. Hayashi, M. Yamasaki, and Y . Morino, Experientia, 1978, 34, 1092; V. F. Zarytova and E. A. Sheshegova, Bioorg. Khim., 1978,4, 901 (Chem. Abs., 1978, 89, 180 277). J. V. O’Connor, H. A. Nunez, and R. Barker, Biochemistry, 1979, 18,500; A. S. Serianni, J. Pierce, and R. Barker, ibid., p. 1192; J. V. O’Connor, Diss. Abstr, Int. B, 1978,39,2786.

l4 T . R. Tritton and I. M. Armitage, Nucleic Acids Res., 1978, 5, 3855; S. Ogawa, R. G. Shulman, P. Glynn, and T. Yamane, Biochem. Biophys. Acta, 1978,502,45; R. G. Shulman, G. Navon, S. Ogawa, and T. Yamane, Deu. Bioenerg. Biomembr., 1977, No. 1, Bioenerg. Membr., p. 471; M. C. Blok, K. J. Hellingwerf, and R. Kaptein, Biochim. Biophys. Acta, 1978,514, 178. M. M. Dhingra, R. H. Sarma, S. Uesugi, and M. Ikehara, J. Am. Chem. Soc., 1978, 100, 4669; J. Granot, ibid., p. 6745; P. H. Bolton and G. Bodenhausen, ibid., 1979, 101, 1080; S. Uesugi, W. Limn, and M. Ikehara, Chem. Pharm. Bull., 1978,26, 3732; D. M. Cheng, M. M. Dhingra, and R. H. Sarma, Nucleic Acids Res., 1978, 5, 4399; C. Altona, A. J. Hartel, and C. S. M. Olsthoorn, Jerusalem Symp. Quantum Chem. Biochem., 1978, No. 11, Nucl. Magn. Resonance Spectrosc. Mol. Biol., p. 87; C . F. G. C. Geraldes and R. J. P. Williams, Eur. J. Biochem., 1978, 85, 463; I. D. Bobruskin, N. N. Gulyaev, and M. P. Kirpichnikov, MoZ. Biol. (Moscow), 1979, 13, 118 (Chem. Abs., 1979, 90, 134 140); M. Borzo and P. Laszlo, C. R. Hebd. Seances Acad. Sci., Ser. C., 1978, 287, 475; F. Inagaki, T. Miyazawa, and M. Miwa, Biochem. Biophys. Res. Commun., 1978,85,415; M. Maccoss, F. S. Ezra, and M. J. Robins, Curbohydr. Res., 1978, 62,203; F. E. Evans, C.-Y. Lee, and H. Kapmeyer, Bioorg. Chem., 1978,7,57; W. H. Dawson and R. L. Cargill, J. Curbohydr., Nucleosides, Nucleotides, 1977,4, 363; J. Peeling, F. E. Hruska, and P. C. Loewen, Can. J. Chem., 1978,56, 522.

16 P. B. Kingsley and G. W. Feigenson, FEBS Lett., 1979,97,175; K. E. Falk and B. Karlsson, ibid., 1979, 98, 2 5 ; K. Gawrisch, K. Arnold, T. Gottwald, and G. Klose, Stud. Biophys., 1978, 74, 13; L. Trahms and E. Boroske, Biochim. Biophys. Acta, 1979, 552, 189; J. De Bony, J. Dufourcq, and B. Clin, ibid., p. 531 ; G. Klose, G. Hempel, and T. Von Zglinicki, Chem. Phys. Lipids, 1978, 21, 261; A. Marker, L. G. Paleg, and T. M. Stopswood, ibid.. 1978, 22 39; J. G. Lammers, T. J. Liefkens, and J. Bus, ibid., p. 293; A. C. McLaughlin, C. Grathwohl, and R. E. Richards, J. Magn. Reson., 1978, 31, 283.

l7 I. K. O’Neill and B. Stuart, Org. Magn. Reson., 1978, 11, 533.

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Physical Methods 249

acetylacetonate as the relaxing agent. l8 Nuclear magnetic shielding tensors for phosphine and the dimethyl phosphate anion have been calculated. l9

B P ofPII compounds. The phosphorus atom of the phosphole anion (1) and that of its benzo analogue resonate downfield (SP 73.5 and 81.7 respectively)ao of those of dialkylphosphides 21 and towards the shifts (SP 210-238) recorded for p,-bonded molecules such as the diazaphospholine (2), 2 2 phosphabenzene,2a and the acyclic compound (3).23

(1) (2) (3) (4 1 8p of PII1 compounds. Large deuterium isotope effects have been observed

for p h ~ s p h i n e . ~ ~ The 6~ values determined from the satellites in the spectra of the diphosphine (4) show 13C isotopic shielding effects of 0.004 p.p.m. through two bonds and 0.062 p.p.m. through one bond.25 A stereochemical study of the phosphorinan (5) showed that B P is at lower field when the phenyl group is axial, as shown.26 A similar study of the dioxaphosphorinans (6) showed B P to be very sensitive to the presence of axial methyl groups in the y-p~s i t ion .~~ The very large shifts (over 70 p.p.m.) of B P which are shown by the diphosphirans (7) have been attributed to changes in the bond angles with the steric require- ments of R.28 The values of BP for the phosphines (8; Y=PPh,) have been correlated with BC (methyl) for the alkylsilanes (8; Y = Me),29 and the effects of replacing alkyl or aryl by SR groups30 or by trifluorovinyl groups31 in PI11 compounds have been reported. Phosphorus-31 data have been given for numerous diphosphine monoxides. 3 2

18 F. Kasler and M. Tierney, Mikrochim. Acta, 1978, 11, 411. 19 F. R. Prado, C. Giessner-Prettre, B. Pullman, and J. P. Daudey, J. Am. Chem. SOC., 1979,

101, 1737; J. Ridard, B. Levy, and P. L. Millie, Mol. Phys., 1978, 36, 1025. 20 L. D. Quin and W. L. Orton, J. Chem. SOC., Chem. Commun., 1979,401. 21 B. W. Bangerton, R. P. Beatty, J. K. Konba, and S. S . Wreford, J. Org. Chem., 1977, 42,

3247. 22 P. Friedrich, G. Huttner, J. Luber, and A. Schmidpeter, Chem. Ber., 1978, 111, 1558;

V. V. Negrebetskii, L. Ya. Bogel'fer, R. G. Bobkova, N. P. Ignatova, and N. I. Shvetsov- Shilovskii, Zh. Strukt. Khim., 1978, 19, 64 (Chem. Abs., 1978, 89, 5575); A. J. Ashe, R. B. Sharp, and J. W. Tolan, J. Am. Chem. SOC., 1976, 98, 5451.

23 T. C. Klebach, R. Lourens, and F. Bickelhaupt, J . Am. Chem. SOC., 1978,100,4886. 24 A. K. Jameson and C. J. Jameson, J. Magn. Reson., 1978, 32,455; C. J. Jameson and A.

K. Jameson, J. Chem. Phys., 1978, 69 615. z5 R. Paasonen, J. Enqvist, M. Karhu, E. Rahkamaa, M. Sundberg, and R. Uggla, Org.

Magn. Reson., 1978, 11, 42. 26 G. D. MacDonell, K. D. Berlin, J. R. Baker, S. E. Ealick, D. van der Helm, and K. L.

Marsi, J. Am. Chem. SOC., 1978, 100, 4535. 27 E. E. Nifant'ev, S. F. Sorokina, and A. A. Borisenko, J . Gen. Chem. USSR (Engl. Transl.),

1978,48,2158 (Chem. A h . , 1979, 90, 86 203). 28 M. Baudler and F. Saykowski, 2. Naturforsch., Teil B, 1978, 33, 1208. 29 M. Capka, J. Schraml, and H. Jancke, Collect. Czech. Chem. Commun., 1978,43, 3347. 30 E. A. Krasil'nikova, Rum. Chem. Rev. (Engl. Transl.), 1977, 46, 861.

H. G. Horn, R. Koentges, F. Kolkmann, and H. C. Marsmann, 2. Naturforsch., Teil By 1978. 33. 1422; H. G. Horn and F. Kolkmann. ibid., p. 1427.

32 M. Volkholz, 0. Stelzer, and R. Schmutzler, Chem. Ber., 1978,111,890; I. F. Lutsenko and V. L. FOSS, Vestn. Mosk. Univ., Khim., 1978, 19, 379 (Chem. Abs., 1979, 90, 21 707).

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250 Organophosphorus Chemistry

Sp ofPIV compounds. Oxygen-18 isotope shifts on 8p were 0.02 p.p.m. to high field, per oxygen atom, for inorganic phosphate and 0.025 p.p.m. for adenosine S-pho~phate .~~ With the increase in synthetic applications of quasiphosphonium salts, there has been increased interest in their n.m.r. proper tie^.^^ The phosphole oxide and sulphide (9) have remarkably similar chemical shifts.35 This may be due to combined electronic and steric effects. As noted before (Volume 8), the inclusion of the phosphorus atom in a small ring, e.g. three-membered, can have some quite large shielding effects.3s The changes caused by S-methylation of thioph~sphinates,~~ by the generation of the lithium and copper derivatives of phosphonates and by the protonation of tri-t-butylphosphinimine 39 have been reported. A study of the thiophosphoryl bromides (11) showed that SP increases linearly with the number of /3-methyl groups.4o There is quite a large shift in SP for the ylide (12) when the size of the disilane ring is altered, i.e. b p is 6.7 for (12; n=2) and - 10.3 for (12; n= l).4f

QP of P V compounds. Solid mono- and di-arylchlorophosphoranes give narrow 31P n.m.r. signals from which the P I V + Pv structures have been e~t imated .~~ The phosphorus of the selenadioxaphosphorane (1 3 ; X = CF,) resonates well downfield, at SP +26.1,43 in the same region as that of the dithiadioxaphos- p h o r a n e ~ . ~ ~ Some dihalogenotrioxaphosphoranes (14) have been prepared;

33 G. Lowe and B. S. Sproat, J. Chem. SOC., Chem. Commun., 1978, 565. 34 H. Teichmann and J. Gloede, Phosphorus Sulfur, 1978,5, 15; J. Michalski, J. Mikolajczak,

and A. Skowronska, J. Am. Cliem. SOC., 1978, 100, 5386; E. S. Lewis, B. J. Walker, and L. M. Ziurys, J. Chem. SOC., Chem. Commun., 1978,424.

35 F. Mathey and D. Thavard, Can. J . Chem., 1978,56, 1952; F. Mathey and G. Muller, ibid., p. 2486.

3t3 H. Quast and M. Heuschmann, Angew. Chem., Int. Ed. Engl., 1978, 17, 867; G. V. Roe- schenthaler, K. Sauarbrey, and R. Schmutzler, Chem. Ber., 1978, 111, 3105.

37 A. Barabas, F. Popescu, V. Muresan, and L. Almasi, Org. Magn. Reson., 1977, 10, 35. s8 F. Mathey and P. Savignac, Tetrahedron, 1978, 34, 649.

W. Wolfsberger, 2. Naturforsch., Teil B, 1978, 33, 1452. 40 W. Peters and G. Haegele, Phosphorus Sulfur, 1978, 4, 149. 41 H. Schmidbaur and M. Heimann, Chem. Ber., 1978,111, 2696.

B. V. Timokhin, V. I. Dmitriev, and V. I. Glukhikh, J . Gen. Chem. USSR (Engl. Transl.), 1978,48, 1305 (Chem. Abs., 1979,90,21 724).

4s K. Burger, R. Ottlinger, A. Frank, and U. Schubert, Angew. Chem., Int. Ed. Engl., 1978, 17, 774. B. C. Burros, N. J. De’ath, D. B. Denney, D. Z. Denney, and I. J. Kipnis, J. Am. Chem. SOC., 1978, 100, 7300; A. C. Sau and R. R. Holmes, J. Organomet. Chem., 1978, 156, 253.

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Physical Methods 251 the dichloro-compound (14; X= C1) has BP - 35, whereas the dibromophos- phorane (14; X=Br) has B P - 195,45 well upfield of the resonances of most Pv compounds.

BP of Pvl compounds. The interesting diazadiphosphetidine (1 5) has B P - 155.46

Fluorine-19. The transmission of electronic effects in triarylphosphines (1 6 ) has been studied by ISF n.m.r. spectros~opy.~~ A study of salts of the phosphonium ion (17) showed BF and JPCF to be linearly related to the electronegativities of Y and Z,48 and, for the phosphoranes (18), BF had nearly a linear correlation with J P F . ~ ~ An investigation of the changes in 8~ and YCF in perfluorinated phosphine oxides that were induced by the addition of alcohol indicated that the a-difluoromethyl group competes with the phosphoryl oxygen as a site for hydrogen-bonding.

Nitrogen-14 and -15. The factors affecting nuclear shielding of nitrogen-14 nuclei have been investigated for a series of aminophosphines. 51 The association of some 1,2,3-diazaphospholes has been studied by lH, 14N, and 15N n.m.r. spectros~opy.~~ Carbon-13. The changes in Sc for a series of phosphorinans (19) have been attributed to y- and d-efl'ect~.~~ The electronic effects of the PH2, PF2, and

45 J. Michalski, J. Mikolajczak, M. Pakulski, and A. Skowronska, Phosphorus Sulfur, 1978, 4,

46 W. Meindl and K. Utvary, Monatsh. Chem., 1979, 110, 129. 47 S. I. Pombrik, V. F. Ivanov, A. S. Peregudov, D. N. Kravtsov, and A. A. Fedorov, J .

48 M. J. van Hamme and D. J. Burton, Org. Magn. Reson., 1978, 11, 275. 49 H. B. Stegman, €3. V. Dumm, and K. Scheffler, Phosphorus Sulfur, 1978, 5, 159. 50 V. Ya. Semenii, V. N. Zavatskii, N. N. Kalibabchak, E. V. Ryl'tsev, and V. V. Malovik,

51 K. Barlos, H. Noeth, and B. Wrackmeyer, 2. Naturforsch., Teil B, 1978, 33, 515. 52 V. V. Negrebetskii, L. Ya. Bogel'fer, A. V. Vasil'ev, R. G. Bobkova, N. P. Ignatova, N. I .

Shvetsov-Shilovskii, and N. N. Mel'nikov, Zh. Strukt. Khim., 1978, 532 (Cliem Abs., 1978, 89, 196 485).

53 E. E. Nifant'ev, A. B. Borisenko, S. F . Sorokina, M. K. Grachev, and A. I. Zavalishina, J . Gen. Chem. USSR (Engl. Transl.), 1977, 47, 2262 (Chem. Abs., 1978, 88, 61 897).

233.

Organomet. Chem., 1978,153, 319.

J . Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1213.

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252 Organophosphorus Chemistry

Y I R N q P

' c k I M e ,

(19)

PCl, groups5* and of the PMe, group55 have been calculated from 6c values, and there have been further studies of bonding in stabilized phosphonium ylides and their Equilibria and Shift Reagents.-The positions of tautomeric6' and isomeric eq~i l ibr ia ,~~ as determined by n.m.r., have been used to estimate conformational free energies of ring substituents in phosphorin derivatives. The kinetic acidities of protonated phosphines in water and dimethyl sulphoxide have been studied by lH n.m.r.69 A variable-temperature lH n.m.r. study of the cyclo-octatetraenes (20; R= Et, But, or Ph) led to detailed information on the dynamics of migration of double bonds, of ring inversion, and of rotation about the P-C (ring) bond.6o N.m.r. studies have also been published concerning dyadic tautomerism and the site of attack by electrophiles on salts of the ion (21),61 and the PIV+Pv equilibria of chlorophosphoranes.6

Shift reagents have been used in stereochemical studies of bicyclic phosphine vinylpho~phonates,~~ and the spirophosphorane (22).s6 The use of

lanthanide shift reagents for the detection of the (R)- and (S)-enantiomers of isophosphamide by S1Pn.m.r.66 and in a wider study of chiral compounds (mainly phosph~nates)~~ has been reported. There have also been studies of competing sites for Eu(fod), with phosphonyl carboxylates 88 and a comparison of the effectiveness of several shift reagents with macrocyclic phosphonate~.~~ 54 W. J. E. Parr, J. Chem. SOC., Faraday Trans. 2, 1978, 74, 933. 55 A. Ricci, F. Bernardi, R. Danieli, D. Macciantelli, and J. H. Ridd, Tetrahedron, 1978, 34,

56 G. Fronza, P. Bravo and C. Ticozzi, J. Organomet. Chem., 1978,157, 299. 57 B. A. Arbuzov, 0. A. Erastov, S. N. Ignat'eva, T. A. Zyablikova, and E. I. Gol'dfarb.,

58 B. A. Arbuzov, 0. A. Erastov, and S. Sh. Khetagurova, Bull. Acad. Sci. USSR, Div. Chem

59 B. Bianchin, J. Chrisment, J. J. Delpuech, M. B. Deschamps, D. Nicole, and G. Serratrice,

6o A. W. Spiegl and R. D. Fischer, Chem. Ber., 1979, 112, 116. 61 T. A. Mastryukova, I. M. Aladzheva, I. V. Leont'eva, V. A. Svoren, P. V. Petrovskii, and

M. I. Kabachnik, J. Gen. Chem. USSR (Engl. Transl.), 1977,47, 2239, 2243 (Chem. Abs., 1978, 88, 74 435, 88 887).

62 B. V. Timokhin, V. 1. Dmitriev, V. I. Glukhikh, and N. A. Korchevin, Bull. Acad.Sci USSR, Div. Chem., Sci., 1978,27, 1160 (Chem Abs., 1978, 89, 196 763).

63 M. Rotem and Y. Kashman, Tetrahedron Lett., 1978, 63. 64 G. A. Berkova, V. I. Zakharov, B. I. Ionin, and A. A. Petrov, J. Gen. Chem. USSR (Engl.

Transl.), 1978, 48, 54 (Chem. Abs., 1978, 88, 151 904). 65 B. Garrigues and D. Houalla, Bull. SOC. Chim. Fr., Part 2, 1978, 65. 66 S. M. Ludeman, D. L. Bartlett, and G. Zon, J. Org. Chem., 1979, 44, 1163. 67 I. V. Galakhov, 0. V. Verenikin, and I. L. Knunyants, Zh. Vses. Khim. Ova., 1978, 23, 234

68 K. B. Yatsimirskii, N. K. Davidenko, V. A. Bidzilya, and L. P. Golovkova, Koord. Khim.,

69 K. B. Yatsimirskii, V. A. Bidzilya, L. P. Golovkova, and A. S. Shtepanek, Dokl. Akad.

+

193.

Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978, 27, 1339 (Chem Abs., 1979, 90, 5794).

Sci., 1978, 27, 1682 (Chem Abs., 1978, 89, 196 862).

Chem. Abs., 1979,90, 120 775.

(Chem. Abs., 1978,89, 59 364).

1978, 4, 1306 (Chem. Abs., 1978, 89, 206 931).

Nuuk SSSR, 1979,244, 1142 (Chem. Abs., 1979, 90, 185 911).

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Physical Methods 253

Variable-temperature Studies.-Pseudorotation. There continues to be much interest in the dynamic properties of pentaco-ordinate phosphoranes 70 (see also Chapter 2). Restricted Rotation. In addition to the commonly observed dynamic behaviour- involving restricted rotation about the P--N bonds of phosphines and phos- p h o r a n e ~ , ~ ~ two (13C)carbonyl resonances (in a ratio of 2 : 1) have been observed in the spectra of triaroylphosphines, and attributed to contributions by amide- like canonical structures (23).7 Comparative n.m.r. studies and force-field calculations of d i ~ i l a n e s ~ ~ indicate that lone-pair gauche effects may not be an important factor in the restricted rotation of diph~sphines.~~ The observation that the (Me,Si),CH group is more effective than the Me,C group for increasing the barrier to P-C bond rotation, but that the reverse applies to P-N bond rotation, may be related to a change in the geometry of the N-~ubstituents.~~ Inversion. Evidence has been presented that the threshold dynamic process of tridurylphosphine is inversion.76 Configuration and Medium Effects.-The study of chiral organophosphorus compounds by n.m.r. spectroscopy has proved quite successful. The absolute configurations of the thio-acids (24) have been determined from the n.m.r.

70 G. V. Roeschenthaler, Z. Nuturforsch., Teil B, 1978, 33, 31 1 ; H. Schmidbaur and P. Holl, ibid., p. 489; G. V. Roeschenthaler and K. Sauerbrey, ibid., 1979, 34, 107; R. D. Gareev, G. M. Loginova, Yu. Yu. Samitov, and A. N. Pudovik, J. Gen. Chem. USSR (Engl. Transl.), 1977,47,2431 (Chem. Abs., 1978,88, 135 852); V. V. Ragulin, N. A. Razumova, andV. I. Zakharov, Khim. Prakt. Pimenenie Kremnii Fosfororg. Soedin., 1977, 3 (Chem. Abs., 1978, 89, 128 989); J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 650 (Chern. Abs., 1978, 89, 43 609); V. V. Ragulin, Tezisy Dokl. Resp. Konf. Molodykh Uch.-Khim., 1977, 52 (Chem. Abs., 1978, 89, 109 791); S. Antczak and S. Trippett, J. Chem. SOC., Perkin Trans. I , 1978, 1326; H. B. Eikmeier, K. C. Hodges, 0. Stelzer, and R. Schmutzler, Chem. Ber., 1978,111, 2077; D. Hellwinkel, W. Lindner, and W. Schmidt, ibid., 1979, 112, 281; D. Hellwinkel and W. Krapp, ibid., p. 292; R. G. Cavell, J. A. Gibson, and K. I. The, Inorg. Chem., 1978, 17, 2880.

71 Yu. Yu. Samitoy, M. A. Pudovik, and A. N. Pudovik, J. Gen. Chem. USSR (Eltgl. Transl.), 1978,48,1552 (Chem. Abs., 1978,89,179 412); 0. J. Scherer and K. Andres, Z. Naturforsch., Teil B, 1978,33,467; S . C . Peake, M. J. C. Hewson, 0. Schlak, R. Schmutzler, R. K. Harris, and M. 1. M. Wazeer, Phosphorus Sulfur, 1978, 4, 67.

72 G. D. MacDonell, A. Radhakrishna, and K. D. Berlin. Tetrahedron Lett., 1978, 857. 73 S. G. Baxter, D. A. Dougherty, J. F. Blount, and K. Mislow, J. Am. Chem. Soc., 1978,100,

7795; K. Mislow, D. A. Dougherty, and W. D. Hounshell, Bull. SOC. Chim. Belg., 1978,87, 555.

7 4 I. F. Lutsenko and M. V. Proskurina, Russ. Chem. Rev. (Engl. Trunsl.), 1978,47, 880. 75 H. Goldwhite and P. P. Power, Org. Magn. Reson., 1978, 11, 499. 76 V. V. Negrebetskii, A. I. Bokanov, and L. Ya. Bogel'fer, J. Gen. Chem. USSR (Engl.

Transl.), 1978, 48, 1196 (Chern. Abs., 1978, 89, 107 698).

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254 Organophosphorus Chemistry

spectra of their (-)-1-phenylethylamine salts in polar solvents such as pyridine." The diastereoisomers of the diphosphine (25) and its diselenide have been identified by the isochronous property of the methylene protons of the racemate, which are readily distinguished from the diastereotopic methylene protons of the rne~o-forrn.~~ The diastereoisomers of the heterocycle (26) were distinguished by the presence of two 31P signals.79 Further work has been completed on the non-equivalence induced by optically active phosphinothioic acids,80 and the SCADA interpretation has been reviewed.81 Chiral centres were also the source of non-equivalence in the 31P and 19F n.m.r. spectra of l-aminophosphonateaS and the thiophosphorus compounds (27; X = F or CF3).83

There have been several n.m.r. studies of phosphorus compounds in liquid crystals (nematic phase), and 31P anisotropies, together with stereochemical information, have been obtained for pho~phabenzene,~~ tris(dimethylamin0)- p h ~ s p h i n e , ~ ~ and a cyclotetraphosphine.86 The 31P anisotropies of a solid phosphoryl compound with C32( symmetry have also been determined.*' Shifts of SP of polyphosphates caused by Mg2+ ions support a conformational dependence on the counter-ion.8s Spin-Spin Coupling. The lH n.m.r. spectra of the protonated diphosphine (28) have been measured between -65 and +75"C and found to be useful for the study of the XnAA'Xn spin systems.8g

JPP and JPM. Many organophosphorus compounds which contain two or more phosphorus atoms have been prepared?O and most give very informative

7 7 M. Mikolajczyk, J. Omelanczuk, M. Leitloff, J. Drabowicz, A. Ejchart, and J. Jurczak, J.

78 I. J. Colquhoun and W. McFarlane, J. Chem. Res. (S ) , 1978, 368. 79 J. B. Robert and H. Weichmann. J. Org. Chem., 1978, 43, 3031.

Am. Chem. Sac., 1978,100, 7003.

M. J. P. Harger, Tetrahedron Lett., 1978, 32, 2927; M. J. P. Harger, J. Chem. Soc., Perkin Trans. 2, 1978, 326. M. I. Kabachnik, T. A. Mastryukova, E. I. Fedin, M. S . Vaisberg, L. L. Morozov, P. V. Petrovskii, and A. E. Shipov, Rim. Chem. Rev. (Engl. Transl.), 1978, 47, 821.

A. Kotynzki and W. J. Stec, J. Chem. Res. (S ) , 1978, 41. 83 R. G. Cave11 and L. F. Doty, Inorg. Chem., 1978, 17, 3086. 84 T. C. Wong and A. J. Ashe, J. Mol. Struct., 1978, 48, 219. 85 A. Cogne, J. B. Robert, and L. Wiesenfeld, Chem. Phys. Lett., 1978, 57, 627. 86 J. P. Albrand, A. Cogne, and J. B. Robert, J. Am. Chem. Soc., 1978, 100, 2600. 87 A. R. Grimmer, Spectrochim. Acta, Part A , 1978, 34, 941. 88 T. Glonek, Phosphorus Sulfur, 1978, 4, 235. a9 H. H. Karsch, Z. Naturforsch., Teil B, 1979, 34, 31. 90 M. Baudler, M. Warnau, and D. Koch, Chem. Ber., 1978, 111, 3838; M. I. Kabachnik, A.

A. Prishchenko, Z. S. Novikova, and I. F. Lutsenko, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1088 (Chem. Abs., 1978,89, 197 646); A. Schmidpeter and J. Hoegel, Chem. Ber., 1978, 111, 3867; M. Baudler and H. Heumueller, 2. Anorg. Allg. Chern., 1977, 437, 73; G. Fritz and R. Uhlmann, ibid., 1978, 442, 106; K. Issleib and P. Thorausch, Phosphorus Sulfur, 1978,4, 137; J. P. Albrand and J. B. Robert, C.R. Hebd. Seances Acad. Sci., Ser. C , 1978, 287, 89.

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Physical Methods 255

slP n.m.r. data. The direct P-P coupling is often large but the 503 Hz coupling for the methiodide (29) is of an exceptional rnagni t~de.~~ A wide variety of PNP couplings (20-76 Hz) have been recorded.92 Examples of PCP couplings have been observed which are exceptionally large, e.g. 132 Hz for (30),g3 or exception- ally small, e.g. 19 Hz for (31),94 compared to the usual range of 60-90 Hz.

Large PCCP couplings (1 10-212 Hz) for some diphosphinocarbaboranes have been estimated by a linewidth p r o ~ e d u r e . ~ ~ There has been considerable interest in the structural dependences of P-Se couplings, which may vary within the range 400-1100 Hz.96p97 This coupling, which has been used to estimate conformational populations of cyclic pho~phites,~~ decreases rapidly upon weakening the P-Se bond.98

JPF, JPO, JPN, and J ~ B . There are further examples of the dependence of JPF on the orientation of the P-F bond in fluoroph~sphoranes.~~ Studies of 16N- enriched compounds showed that JPW is in the range 50-90Hz for amino- phosphines and 34-51 Hz for p h o ~ p h a z e n e s ~ ~ ~ ~ ~ ~ and the phosphorane (1Qd9 The negative sign of the reduced P--170 coupling for methyl phosphites fits the general tendency for KPY (Y = B, C , N, 0, or F) to move towards a more negative value for more electronegative elements. This is attributed to a reduced s-overlap

g1 K. Issleib, P. Thorausch, and H. Meyer, Org. Mugn. Reson., 1977, 10, 172. 92 E. P. Flindt, Z. Anorg. Allg. Chem., 1978,447,97; 0. J. Sclierer, G. Sclinabl and T. Lenhard,

ibid., 1979, 449, 167; N. P. Grechkin, L. K. Nikonorova, N. S. Tutova, I. A. Nuretdinov, and L. A. Zhelonkina, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1194; S. S. Krishna- murthy, A. C . Sau, A. R. V. Murthy, R. Keat, R. A. Shaw, and M. Woods, J. Chem. SOC., Dalton Trans., 1977, 1980; D. J. Lingley, R. A. Shaw, M. Woods, and S . S . Krishnamurthy, Phosphorus Surfur, 1978, 4, 379; S. S. Krishnamurthy, K. Memachandren, A. C. Sau, M. N. S. Rao, A. R. V. Murthy, R. Keat, and R. A. Shaw, ibid., 1978,5,117; H. Schmidbaur and P. Holl, Z . Naturforsch., Teil B, 1978, 33, 572; W. Krueger and R. Schmutzler, Inorg. Chem., 1979, 18, 871.

93 R. Appel and G . Erbelding, Tetrahedron Lett., 1978, 2689. 94 T. A. Mastryukova, I. V. Leont'eva, and I. M. Aladzheva, J. Gen. Chem. USSR (Engl.

Transl.), 1978,48, 904 (Chem Abs., 1978, 89, 109 749). 95 W. E. Hill and L. M. Silva-Trivino, Inorg. Chem., 1979, 18, 361, 2495. g6 I. A. Nuretdinov, E. I. Loginova, and E. V. Bayandina, J . Gen. Chem. USSR (Engl. Transl.),

1978,48,975 (Chem. A h . , 1978,89,42 183); I. A. Nuretdinov, N. A. Buina, E. V. Bayandina, E. I. Loginova, and M. A. Giriyatullina, Bull. Acud. Sci. USSR, Div. Chem. Sci., 1978, 27, 378 (Chem. Abs., 1978, 88, 170 247); P. A. W. Dean, Can. J. Chern., 1979, 57, 754.

97 R. D. Kroshefsky, R. Weiss, and J. G. Verkade, Inorg. Chem., 1979, 18, 469. 98 S. 0. Grim, E. D. Walton, and L. C . Satek, Inorg. Chim. Acta, 1978, 27, L115; I. A.

Nuretdinov, D. N. Sadkova, and E. V. Bayandina, Bull. Acad. Sci. USSR, Diu. Chem. Sci., 1977, 26, 244 (Chem A h . , 1978, 88, 50 977); I. A. Nuretdinov, N. A. Buina, and E. V. Bayandina, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 977.

99 E. S. Kozlov, L. G. Dubenko, and M. 1. Povolotskii, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1734 (Chem. Abs., 1978, 89, 163 668); M. Fild, R. Kurpat, and T. Stankiewicz, 2. Anorg. Allg. Chem., 1978,439,145; N. T. Yap and R. G. Cavell, Inorg. Chem., 1979,18, 1301.

100 B. Thomas and G. Grossman, 2. Anorg. Allg. Chem., 1979,448, 107.

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256 0 rganop hosp horus Chemistry

for the P-Y bond, leading to a progressive breakdown of the mean-excitation- energy approximation which is often used in the description of the Fermi-contact interaction.lo1 The first example of a PNB coupling has been described.loa

JPC. INDO calculations of ~JPC require orbital or spin dipolar terms to be included with Fermi-contact terms in order to obtain good agreement with experimental data.lo3 On the other hand, the direct P-C coupling constant for a series of phosphonates (32) and tetrafluorophosphoranes (33) varied linearly with the s-character of the P-C bond, i.e. as R varied through the series ethyl, vinyl, and ethynyl.lo4 Some further examples of large P-C(sp3) couplings (162-188 Hz) have been observed for the phosphonates (34)lo6 and 191.2 Hz for the phosphonamide (35).lo6 In contrast, the oxide (36) has ~JPC as low as 12.5 Hz. 36 Studies of glycosyl phosphonates have indicated that ~JPC (equatorial) exceeds ~JPC (axial) by 19-23 Hz.lo7

0

'OY rm, C'

The geminal PCC coupling constant in allenic phosphonyl compounds is quite low (0-5 Hz),lo8 and a study of some bicyclic compounds (37) showed 2 J ~ ~ to be strongly dependent on steric relationships, but there was no simple correlation with dihedral angle. log The coupling data for some (p-aminoviny1)- phosphonium salts have been reported, and included some surprising vicinal couplings.11o An ab initio CSF study of JPOC in phosphates indicated that the coupling is negative and dependent upon rotation about the P-0 bond.llo As expected, the calculations indicate a positive 3 J ~ ~ ~ ~ and a Karplus relation- ship with dihedral angle, but the magnitude was also dependent upon the rotation about the P-C bond;llO cf. a conformational study of phosphorylated sugars.111 There has also been a truncated Fourier series analysis on the effect of

101 102 103

104 105

106

1 0 7

108 109

110

111

1 1 2

P-0 bond rotation in dimethyl methylphosphonate.l12 The vicinal POCC

H. C. E. McFarlane and W. McFarlane, J, Chem. SOC., Chem. Commun., 1978, 531. H. Binder and J. Palmtag, Z . Naturforsch., Teil B, 1979, 34, 179. M. D. Beer and R. Grinter, J. Magn. Reson., 1978, 31, 187. W. Althoff, M. Fild, H. P. Rieck, and R. Schmutzler, Chem. Ber., 1978, 111, 1845. M. Mikolajczyk, A. Zatorski, S. Grzejszczak, B. Costisella, and W. Midura, J. Org. Chem., 1978, 43, 2518. S. Scheibye, B. S. Pedersen, and S. 0. Lawesson, Bull. SOC. Chim. Belg., 1978, 87, 229, 299. J. Thiem, B. Meyer, and H. Paulsen, Chem. Ber., 1978, 111, 3325. G. A. Krudy and R. S. Macomber, J. Org. Chem., 1978,43, 4656. A. Rudi and Y . Kashman, Org. Magn. Reson., 1977, 10, 245. M. A. Calcagno and E. E. Schweizer, J. Org. Chem., 1978, 43, 4207, S. Samaan, Justus Liebigs Ann. Chem., 1979,43; C. Giessner-Prettre and B. Pullman, J. Theor. B i d , 1978,72, 751. E. E. Nifant'ev, L. T. Elepina, and A. A. Borisenko, J. Gen. Chem. USSR (Engl. Trans[.), 1978,48, 2227 (Chem. Abs., 1979,90, 152 479). B. J. van der Veken and M. A. Herman, J. Mol. Struct., 1978, 44, 245.

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Physical Methods 257 7

(37) (39)

coupling in vinyl phosphates is also strongly dependent on the (E) or (2) con- figuration of substituents in the vinyl g r 0 ~ p . l ~ ~ Other stereochemical studies involving vicinal P-C couplings have been reported for phosphoramidatesy114 triarylphosphines and their chalcogenides, 1,3,2-dithiaphosphorinans, 116

cyclopropylphosphonates, l7 camphanephosphonates (3 8), l8 and norbornyl- phosphines (39) and their PIV derivatives.llg In the study of the PIrr compounds (39), the dihedral angle corresponding to the minimum for 3 J ~ ~ appeared to depend on the nature of the P-substituents.

JPH. A surprising conclusion from a MIND0/3 study of a series of simple phosphines was that ~JPH is inversely proportional to the percentage s-character of the P-H bond.120 The magnitude of ~JPH for protonated bicyclic phosphites correlated with the calculated net atomic charges on phosphorus.l*l A study of protonated alkyl-aryl-phosphines showed a good relationship between ~ J P H and the size of the substituents.122

J P C ~ H and JPXC~H. Further examples have occurred of the angular dependence of JPCH with the Ch-P-C-H dihedral angle,s8p123 and it has been estimated that the dichloride (40) has JPCH - 1 and -25 Hz when the dihedral angles are 180 and 60" respectively. The geminal PCH2 couplings have also been given for some silylmethylphosphonium salts (18-19 Hz)lZ4 and for the syn and anti configurations of /I-oximinopropylphosphonates (syn, 22-23.5 ; anti, 20.5- 2 2 ' € R ~ ) . ~ ~ ~ The gauche and trans vicinal PCCH coupling constants (3.8 and 11.1 Hz) of the a-nitro-phosphonates (41) were estimated from 360 MHz spectra.128 There have been a number of n.m.r. studies of PIII-vinyl com-

113 G. Szalontai, Org. Magn. Reson., 1977, 10, 63. 114 G. W. Buchanan and F. G. Morin, Can. J. Chem., 1979,57,21. 115 V. V. Negrebetskii, L. Ya. Bogel'fer, A. I. Bokanov, N. A. Rozanel'skaya, and B. I.

Stepanov, Zh. Sfrukf. Khim., 1978,19,628 (Chem. Abs., 1979,90, 5457). 116 A. A. Borisenko, S. F. Sorokina, A. I. Zavalishina, N. M. Sergeev, and E. E. Nifant'ev,

J. Gen. Chem. USSR (Engl. Transl.), 1978,48, 1144 (Chem. Abs., 1978, 89, 107 845). 117 C. E. Griffin, E. Kraas, H. Terasawa, G. W. Griffin, and D. C. Larkin, J . Heterocycl.

Chem., 1978,15, 523. 11* J. Thiem and B. Meyer, Org. Magn. Reson., 1978, 11, 50. 119 L. D. Quin and L. B. Littlefield, J . Org. Chem., 1978, 43, 3508. lZo H. Goetz, G. Frenking, and F. Marschner, Phosphorus Sulfur, 1978,4, 309. lZ1 D. van Aken, A. M. C. F. Castelijns, J. G. Verkade, and H. M. Buck, Red. Trav. Chim.

lZ2 F. Kroch and A. Zschunke, 2. Anorg. Allg. Chem., 1978, 440, 45. 123 0. A. Raevskii, N. G. Mumzhieva, T. A. Zyablikova, A. N. Vereshchagin, E. I. Gritsaev,

and M. M. Gilyazov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978,27,528; 0. A. Raevskii, N. G. Mumzhieva, T. A. Zyablikova, and N. A. Aleksandrova, ibid., p. 723 (Chem. Abs., 1978, 89, 107 784); M. V. Sigalov, V. A. Pestunovich, V. M. Nikitin, A. S. Atavan, and B. F. Kukharev, ibid., p. 1349 (Chem. Abs., 1978, 89, 179 402).

Pays-Bas, 1979, 98, 12.

124 G. Singh and G. S. Reddy, J . Org. Chem., 1979, 44, 1057. 125 P. Livant and M. Cocivera, J. Org. Chem., 1978, 43, 3011. lz6 H. Feuer, W. D. van Buren, and J. B. Grutzner, J. Org. Chem., 1978, 43, 4676.

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258 0 rganop hosp horus Chemistry

pounds 127 and PIV-vinyl compounds,128 to determine their (E) or (2) geometries, and studies of various phosphorinans (42) 129 and (43) 130 and phosphepans (44)131 for conformational analysis. In the latter study, which included TI data, it was suggested that JPOCH may not follow a simple Karplus relationship. Long-range P-H couplings have been reported for a 1 -propynylphosphonate (4JPH 5 H z ) , ~ ~ ~ an allenic phosphine oxide ( 6 J ~ ~ ~ H z ) , ' ~ ~ and a diphenyl- phosphinohomocubane ( 6 J ~ ~ 2 H z ) . ~ ~ ~ Relaxation, CIDNP, and N.Q.R. Studies.-The 13C relaxation times of triphenyl- phosphine have been measured 135 and the mechanism of oxidation of phosphites has been studied by CIDNP.13s

R

(42) (43) (44) (45)

The intermolecular interactions of various phosphoryl compounds with acetonitrile have been studied by 14Nn.q.r.137 A combination of 14N and 35Cl n.q.r. measurements was used to study a series of cyclic PIII compounds (45).138 Other 36Cl n.q.r. studies have applied to phosphoryl and thiophosph&yl 127

128

129

130 131 132 133 134 135 136

137

138

A. S. Kruglov, E. L. Oskotskii, and A. V. Dogadina, J. Gen. Chem. USSR (Engl. Transl.), 1978,48, 1371 (Chem. Abs., 1978,89, 163 672); L. V. Krylov, A. N. Glebov, V. G. Petrov, V. V. Kormachev, and V. A. Kukhtin, ibid., p. 2245 (Chem. A h . , 1979, 90, 120 542). Kh. M. Angelov, T. S. Mikhailova, and V. M. Ignat'ev, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1365 (Chem. Abs., 1978, 89, 163 671); I. V. Konovalova, R. D. Gareev, L. A. Burnaeva, N. V. Mikhailova, N. K. Novikova, and A. N. Pudovik, ibid., p. 1554 (Chem. Abs., 1978,89,163 660); W. E. Krueger and M. B. McLean, J. Org. Chem., 1978,43,2877. G. S . Bajwa, W. G. Bentrude, N. S. Pantaleo, M. G. Newton, and J. H. Hargis, J. Am. Chem. SOC., 1979, 101, 1602; J. Martin and J. B. Robert, Org. Magn. Reson., 1977,9, 637; J. A. Mosbo, ibid., 1978, 11, 281; A. A. Borisenko, S. F. Sorokina, A. I. Zavalishina, and E. E. Nifant'ev, Dokl. Akad. Nauk SSSR, 1978,241,842 (Chem. Abs., 1978,89, 162 948). A. Zschanke, H. Meyer, E. Leissring, H. Oehme, and K. Issleib, Phosphorus Sulfur, 1978,5,8 1. A. C. Guimaraes, J. B. Robert, C. Taieb, and J. Tabony, Org. Magn. Reson., 1978,11,411. H. L. Slates and N. L. Wendler, Chem. Ind. (London), 1975, 430. H. Heydt and M. Regitz, J. Chem. Res. (S) , 1978, 326. J. P. Albarella and T. J. Katz, J. Org. Chem., 1978, 43, 4338. C. A. Wilkie, J , Am. Chem. SOC., 1978, 100, 2288. D. G. Pobedimskii, Sh. A. Nasybullin, A. D. Pershin, and A. L. Buchachenko, Chem. Abs., 1978, 89,23 477; V. A. Kurbatov, D. G. Pobedimskii, E. I. God'dfarb, and A. L. Bucha- chenko, Chem. Abs., 1978, 89, 23 478. A. I. Andreeva, I. Ya. Kuramshin, D. Ya. Osokin, I. A. Safin, and A. N. Pudovik, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1299. I. A. Nuretdinov, 0. N. Nuretdinova, I. A. Safin, and D. Ya. Osokin, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978, 27, 824 (Chem. Abs., 1918, 89, 59 365); Zh. Fiz. Khim., 1979.53, 126 (Chem. Abs., 1979, 90, 177 623).

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chlorides, 139 a wide range of chlorophosphazenes, 140 a benzotrichlorophos- pholan,141 and a trichloromethylphosphorane.gg

2 Electron Spin Resonance Spectroscopy There have been several studies of phosphine radical with questions raised with regard to their stability,143 and indications have been given that they can react with further PII1 molecules to give dimers (46).144 Radicals produced by irradiation of phosphine complexes 145 and by charge transfer 146

have aIso been examined by e.s.r. spectroscopy, as have the radical anions formed by the action of potassium on ary1dipho~phines.l~’ The structures of anion and cation radicals formed polarographically from aryl 148 and vinyl 14@ PIV diphosphorus compounds have also been studied. The e.s.r. spectra of some phosphonyl radicals Y 2P0,160 azaphosphorin radicals,151 and a variety of phosphoranyl radicals 152-164 have been recorded. The pseudorotation aspects 163 and the effect of n-bonds on the structure of phosphoranyl radicals lS4 have been discussed, and the mechanisms of the electron-capture processes have been

139 B. V. Tiniokhin, V. 1. Dmitriev, V. N. Dudnikova, V. P. Feshin, and M. G. Voronkov, Dokl. Akad. Nauk SSSR, 1978,241, 640 (Chem. Abs., 1978, 89, 179 341). V. A. Mokeeva, I. A. Kyuntsel, and G. B. Soifer, Zh. Fiz, Khim., 1978, 52, 2743 (Chem. Abs., 1979,90, 136 894); E. A. Romanenko, M. 1. Povolotskii, N. G. Pavlenko, and Yu. P. Egorov, Teor. Eksp. Khim., 1978, 14, 834 (Chem. Abs., 1979, 90, 103215); K. R. Sridharan, J. Ramakrishna, and S. S. Krishmamurthy, Proc. Nuclear Phys. Solid State Phys. Symp., 1977,20C, 590; P. P. Kornuta, L. S. Kuz’menko, M. V. Vovk, E. A. Roma- nenko, S. V. Iksanova, and L. N. Markovskii, J. Gen. Chem. USSR (Engl. Transl.), 1977, 47,2305 (Chem. Abs., 1978,88, 105 276); P. P. Kornuta and L. S. Kuz’menko, ibid., 1978, 48, 729 (Chem. Abs., 1978, 89, 109 733); P. P. Kornuta and N. V. Kolotilo, ibid., p. 1081 (Chem. Abs., 1978, 89, 109 392); E. S. Kozlov, S. N. Gaidamaka, M. I. Povolotskii, I. A. Kyuntsel’, V. A. Mokeeva, and G . B. Soifer, ibid., p. 1155 (Chem. Abs., 1979, 90, 5401).

I 4 l S. V. Fridland, Yu. K. Malkov, and A. I. Efremov, J . Gen. Chem. USSR (Engl. Transl.), 1978,48, 325 (Chem. Abs., 1978, 88, 190 991).

138 M. B. Zuev, I . D. Morozova, A. V. Il’yasov, and 0. P. Charkin, Izt;. Akad. Nauk SSSR, Ser. Khim., 1978,2293 (Chem. Abs., 1979,90, 12 628); P. Tordo, M. Boyer, F. Vila, and L. Pujol, Phosphorus Sulfur, 1977, 3, 43.

143 W. Kaim, H. Bock, and H. Noeth, Chem. Ber., 1978, 111, 3276. 144 W. B. Gara and B. P. Roberts, J. Chem. SOC., Perkin Trans. 2, 1978, 150. 145 M. C. R. Symons and J. E. Drake, J. Chem. Res. (S) , 1978, 122; T. Berclaz and M. Geof-

146 G. Boekestein and H. M. Buck, Phosphorus Sulfur, 1978,5, 61. 147 W. Kaim and H. Bock, Chem. Ber., 1978,111,3843; W. Kaim and H. Bock, J . Am. Chem.

1*8 C . K. White and R. D. Rieke, J . Org. Chem., 1978,43,4638. 149 A. A. Vafina, A. V. Il’yasov, E. A. Berdnikov, I. D. Morozova, T. R. Tantasheva, and V.

I. Morozov, B~ill. Acad. Sci. USSR, Diu. Clzem. Sci., 1977,26,2306 (Chem. Abs., 1978,88. 88 660). B. P. Roberts and K. Singh, J. Organomet. Chem., 1978, 159, 31.

151 P. P. Kornuta, V. N. Bobkov, and 0. M. Polumbrik, J. Gen. Chem. USSR, (Engl. Transl.), 1978, 48, 639 (Chem. A h . , 1978, 89, 109 723).

15’7 J. A. Howard and J. C. Tait, Can. J. Chem., 1978,56, 2163; M. C. R. Symons, J. Chem Res. (S ) , 1978, 358; B. L. Tumanskii, S. P. Solodovnikov, I. V. Leont’eva, N. N. Bubnov, and M. I. Kabachnik, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1977,26, 1990 (Chem. Abs., 1978, 88, 21 695).

155 V. V. Pen’kovskii, Dokl. Akad. Nauk SSSR, 1978,243,375 (Chem. Abs., 1979,90,71 589); A. Nakanishi and W. G. Bentrude, J. Am. Chen?. SOC., 1978,100,6271 ; R. S. Hay and B. P. Roberts, J. Chem. SOC., Perkin Trans. 2, 1978, 770.

froy, Nelv. Chim. Acta, 1978, 61, 684.

SOC., 1978, 100, 6504.

154 V. V. Pen’kovskii, Teor. Eksp. Khim., 1978, 14, 671 (Chem. Abs., 1979, 90, 71 551).

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260 Organophosphorus Chemistry

discussed in detail.155 E.s.r. spectroscopy has been used for the quantitative estimation of radical mixtures produced by the oxidation of phosphites 156 and to study the influence of protonation or alkylation on the homolytic frag- mentation of monoalkyl phosphates.lS7 E.s.r. spectroscopy is finding a use in the biochemical studies of organophosphorus and there is a corresponding increase in work on spin 1abelli11g.l~~ The e.s.r. spectra of free radicals with a six-co-ordinate phosphorus atom have been described. 160

y36--hY3 Me, P(CF,),-,, (Et,N),P= CHCONEt, Et,PMe,- ,I

(46) (47) (48) (49)

3 Vibrational and Rotational Spectroscopy Band Assignments.-The P-H and P-D bending modes of dimethylphosphine have been re-assigned,l8l and the vibrational spectra of the methyl(trifluorometh- y1)phosphines (47; n= 1 or 2) 162 and trivinylphosphine assigned.ls3 The P=C stretching frequency of stabilized triphenylphosphonium ylides has been identi- fied at 1190 and the C-H stretching frequency of the P=CH group in the ylide (48) shown to occur at about 2900 cm-1 by labelling with Other assignments of vibrational spectra have been reported for methylphosphine oxides,166 diphosphine disulphides,ls7 dimethylphosphinyl compounds, ls8 and triazaphospha-adamantanes. ls9

l55 S. P. Mishra and M. C. R. Symons, Faraday Discuss. Chem. SOC., 1977, No. 63, Radiat. Eff. Liq. Solids, p. 175.

I513 A. Nakanishi, K. Nishikida, and W. G. Bentrude, J. Am. Chem. SOC., 1978, 100, 6398, 6403.

157 G. Behrens, G. Koltzenburg, A. Ritter, and F. D. Schulte, Int. J. Radiat. Biol., 1978, 33, 163.

I58 Y. Kirino, T. Ohkuma, and H. Shimizu, J. Biochem. (Tokyo), 1978, 84, 111; M. C. R. Symons and R. L. Petersen, Biochim. Biophys. Acta, 1978,537,70; A. K. Grover and B. J. Forrest, ibid., 1979,550,212; D. Krilov, A. Velenik, and J. N. Herak,J. Chem. Phys., 1978, 69,2420; D. M. Close and W. A. Bernhard, ibid., 1979,70,210; B. Rakvin and J. N. Herak, Radiat. Res., 1978, 74, 387; K. W. Butler, and I. C. P. Smith, Can. J. Biochem., 1978, 56, 117; M. E. Markes and D. A. Adams, Biomol. Struct. Funct. (Symp), 1977, 109; V. I. Shvets, V. A. Sukhanov, and V. V. Okhanov, Chem. Phys. Lipids, 1979,23, 163.

159 G. V. Roeschenthaler and W. Storzer, Phosphorus Sulfur, 1978, 4, 373; W. Storzer and G. V. Roeschenthaler, 2. Naturforsch, Teil B, 1978, 33, 305; G. Sosnovsky and M . Konieczny, Synthesis, 1978, 8, 583.

160 A. E. Prokof'ev, A. A. Khodak, N. A. Malysheva, P. V. Petrovzkii, V. V. Bubnov, S. P. Solodovnikov, and M. I. Kabachnik, Dokl. Akad. Nauk SSSR, 1978,240,92 (Chem. Abs., 1978, 89, 107 373). A. J. F. Clark and J. E. Drake, Spectrochim. Acta, Part A, 1978,34, 307.

162 R. Demuth, J. Apel, and J. Grobe, Spectrochim. Acta, Part A, 1978, 34, 357, 361. 163 G. Davidson and S. Phillips, Spectrachim. Acta, Part A, 1978, 34, 949. ls4 P. J. Taylor, Spectrochim. Acta, Part A, 1978, 34, 115. 165 L. I. Mizrakh, L. Yu. Polonskaya, and T. M. Ivanova, J. Gen. USSR (EngE. Transl.), 1978,

I6I3 0. L. Alves and Y. Hase, Ecletica Quim., 1978, 3, 35; M. P. McDonald and L. D. R.

167 J. Durig and M. A. Sens, J. Cryst. Mol. Struct., 1977, 7, 295. l 6 8 W. D. Burkhardt, E. C. Hoehn, and J. Goubeau, 2. Anorg. Allg. Chem., 1978, 442, 19;

I69 K. H. Jogun, J. J. Stezowski, E. Fluck. and J. Weidlein, Phosphorus Surfur, 1978, 4, 199.

48, 1733 (Chem. Abs., 1978,89, 197 652).

Wilford, Spectrochim. Acta, Part A, 1978, 34, 933.

H. Schrem and J. Weidlein, ibid., 1978, 444, 135.

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Physical Methods 261

Stereochemistry.-1.r. and Raman spectroscopy have been applied to the con- formational analysis of some ethylphosphines (49; n = 1-3),170 acyldialkyl- phosphines,171 chlorodi~xaphosphepans,~~~ the a-keto-phosphine oxide (50; R = dialkyldiphosphine d i ~ u l p h i d e s , ~ ~ ~ silylalkylpho~phonates,~~~ dichloromethylthiophosphonyl dichloride, 176 and various phosphorinans (5 1 ; Y or Z=CH2 or O).177 The populations of (E) and (2) rotamers of some stabilized ylides have been r e ~ 0 r t e d . l ~ ~ Bonding and Structural Relationships.-Information on lengths and strengths of C-H bonds of the methylphosphines has been obtained from their i.r. Bonding in triarylphosphine oxides has been studied by correlation analysis, using V(PO),~~O and the PIII + PIv structures of the phospholans (52) have been studied in various solvents.lsl The dependencies of the frequencies and the intensities of v(C=C) for the isomeric structures of the phosphinates (53) have been discussed.la2

There have been numerous i.r. studies which involve hydrogen-bonding. The basicities of the phosphoryl group in bicyclic phosphines, as measured by strengths of hydrogen bonds with phenol, have been related to their structures,le3

Ph

0 II

R,PCOR

(50)

Ch II

f

170 C. Crocker and P. L. Goggin, J. Chem. Soc., Dalton Trans., 1978, 388. 171 E. R. Razumova, Yu. I. El’Natanov, Sh. M. Shikhaliev, and R. G. Kostyanovskii, Brill.

Acad. Sci. USSR, Diu. Chem. Sci., 1978, 27, 85 (Chem. A h . , 1978, 89, 23 298). 172 D. F. Fazliev, R. R. Shagidullin, and 0. N. Nuretdinova, Bull. Acad. Sci. USSR, Diu.

Chem. Sci., 1977, 26, 2444 (Chem. Abs., 1978, 88, 36 808). 1 7 3 B. N. Laskorin, V. V. Yakshin, and L. I. Sokal’skaya, Zh. Strukt. Khim., 1978, 19, 757

(Chem. Abs., 1979,90, 55 021). 174 G. P. McQuillan and I. A. Oxton, Spectrochim. Acta, Part A, 1978, 34, 33.

I. A. Lapin, Yu. V. Kolodyazhnyi, E. F. Bugerenko, and 0. A. Osipov, J. Gen. Cheni. USSR (Engl. Transl.), 1978, 48, 2161 (Chem. Abs., 1979, 90, 120 876). N. G. Mumzhieva, N. A. Aleksandrova, A. N. Vereshchagin, and 0. A. Raevski, Bull. Acad. Sci USSR, Diu. Chem. Sci., 1977,26,2189 (Chem. Abs., 1978,88, 37 112).

177 B. A. Arbuzov, R. P. Arshinova, and T. D. Sorokina, Bull. Acad. Sci USSR, Diu. Chem. Sci., 1978,27, 1769 (Chem. Abs., 1979,90,22 186); I. Kh. Shakirov and R. R. Shagidullin, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48 458 (Chem. Abs., 1978,89, 23 639); Y. G. Bosyakov, A. P. Logunov, B. M. Butin, and V, I. Artyukhin, ibid., p. 1189; B. A. Arbuzov, 0. A. Erastov, S. N. Ignat’eva, T. A. Zyablikova, R. P. Arshinova, and I. Kh. Shakirov, Dokl. Akad. Nauk SSSR, 1978,240, 331 (Chem. Abs., 1978, 89, 107 816).

178 1. E. Boldeskul, R. A. Loktionova, L. A. Repina, and V. P. Lysenko, J . Gen. Chem. USSR (Engl. Transl.), 1977, 47, 2490 (Chem. Abs., 1978, 88, 151 898).

179 D. C. McKean and G. P. McQuillan, J. Mol. Struct., 1978, 49, 275. 180 J. M. Casper and E. E. Remsen, Spectrochim. Acta, Part A, 1978, 34, 1 . lS1 V. V. Ovchinnikov, V. I. Galkin, E. G. Yarkova, L. E. Markova, R. A. Cherkasov, and

A. N. Pudovik, J. Gen. Chem. USSR (Engl. Transl.), 1978,48, 2199 (Chem. Abs., 1979,90, 103 185).

lA2 A. V. Fuzhenkova, N. I. Galyautdinov, and B. A. Arbuzov, Bull. Acad. Sci. USSR, Div. Chem. Sci.. 1978 27.982.

lS3 D. S . Milbrath, J. G. Verkade, G. L. Kenyon, and D. H. Eargle, J. Am. Chem. SOC., 1978, 100,3167.

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262 0 rganop hosphor us Chemistry

and the problem of self association of phenol and its effect on the dielectric constant has been discussed. lS4 Hydrogen-bonding has been studied in a-hydroxyphosphoryl compounds, with and without added phenol, lE5 and in a variety of phosphorus acids,186 phenolic derivatives of phosphonates,ls7 and phosphino- or phosphinyl-carboxylic acid derivatives.188 Microwave Spectroscopy.-The rotation barriers of acyclic and cyclic phosphines have been examined by a molecular mechanics treatment and the results com- pared with microwave, i.r., and Raman results. lS9 The conformational analysis of 1,3,2-dioxaphosphorinans by microwave and i.r. spectroscopy and by studies of the Kerr effect was assisted by CND0/2 calculations.1g0

4 Electronic Spectroscopy Absorption Spectroscopy.-The use of third- and fourth-order derivatives in the measurement of absorption spectra maximizes the information available for interpretation. lgl The U.V. spectra of a series of aryldialkylphosphines contain bands which are sensitive to steric effects. The trends observed have been attri- buted to conformational changes. l g 2 9 lg3 The bathochromic shifts observed when P-alkyl groups are replaced by P-aryl groups have been attributed to concurrent increases in CPC bond angles, the p-character of the lone pair of electrons on phosphorus, and the amount of pa In a comparative study of cyano-stabilized methylene- and imino-phosphoranes, the Ph3P=C had more powerful auxochromic properties than the Ph3P=N group.lg4 The absorption maxima of the iminophosphoranes (54) have been correlated with (T@ and

ln4 0. A. Raevskii, M. M. Gilyazov, and Ya. A. Levin, J . Gen. Chem. USSR (Engl. Transl.), 1978, 48, 959 (Chem. Abs., 1978, 89, 107 641). Z. I. Yagnyukova, A. F. Vasil'ev, L. V. Kovalenko, V. V. Galushina, and Yu. A. Strepik- heev, Chem. Abs., 1979,90, 5418; R. G. Islamov, M. G. Zimin, I. S. Pominov, and A. N. Pudovik, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1140; R. R. Shagidullin, E. P. Trutneva, and F. S . Mukhametov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978, 27, 575.

In6 M. Cotrait, E. Dupart, J. Prigent, and C. Garrigon-Lagrange, J. Mol. Struct., 1978, 50, 313; I. P. Lipatova, R. R. Shagidullin, F. M. Kharrasova, S. A. Samartseva, and 2. Z . Kurzhunova, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 77 (Chem. Abs., 1979, 90, 5669); L. I. Katzin, G. W. Mason, and D. F. Peppard, Spectrochim. Acta, Part A , 1978, 34, 51, 57.

187 L. Tusek and V. Jagodic, Croat. Chem. Acta, 1977, 49, 829. lS8 J. Ludvik and J. Podlahova, J. Inorg. Nucl. Chem., 1978, 40, 967; M. P. Sokolov, B. G.

Liorber, A. I. Razumov, V. V. Moskva, Z. Ya. Bulatova, and T. V. Zykova, J. Gen. Chem. USSR (Engl. Transl.) 1978, 48, 940.

R. P. Arshinova. Phosphorus Sulfur, 1978, 5, 131. lS9 N. L. Allinger and H. von Voithenberg, Tetrahedron, 1978, 34, 627.

lgl G. Talsky, L. Meyring, and H. Kreuzer, Angew. Chem., Int. Ed. Engl., 1978,17,532,785. lg2 1. W. Jones and J. C. Tebby, J. Chem. Soc., Perkin Trans. 2, 1979, 501. lg3 G. V. Ratovskii, A. M. Panov, 0. A. Yakutina, Yu. I. Sukhorukov, and E. N. Tsvetkov,

J. Gen. Chem. USSR (Engl. Transl.), 1978,48, 1394 (Chem. Abs., 1978, 89, 162 660). ID'& P. J. Buttefield, J. C. Tebby, and T. J. King, J. Chem. SOC., Perkin Trans. 1, 1978, 1237.

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Physical Methods 263

o d . lg6 The U.V. spectra of the phosphanaphthalene (55),lg6 some triazaphos- phorins, 197 and unsaturated trichlorophosphonium salts lg8 have been described and the highly coloured phosphonium thiolate (56) has been prepared.lg9 Photoelectron Spectroscopy.-The ionization potentials (I.P.) obtained from p.e. spectra have been compared with the energies of the lowest occupied orbitals calculated by the MIND0/3 method.120 The p.e. spectra of A3-phosphorins and of PIII compounds and their chalcogenides have been reviewed,200 and the hybridization and the role of d-orbitals in A3- and i15-phosphorins investigated by HMO calculations.201 The Auger and X-ray p.e. spectra of phosphine and phosphorus trihalides have been compared with calculated data.202 From a study of isomeric bicyclic PI11 compounds (57) and (58) it has been proposed that the

( 5 6 ) (5 7) ( 5 8 )

T.P. of the lone pairs of electrons on phosphorus is less than that of those on oxygen.2o3 The I.P. values of various phosphines have been correlated with CPC bond angleszo4 and with MIND0/3 recalculations of their heats of formation. 205 Variable-temperature p.e. spectra of the diphosphine Me,PPMe2 indicate that the anti conformer is more stable (by 0.5 kcal mol-l) than the gauche conformer.a06 This result contrasts with the preferred gauche con- formation of PzHl recently supported by MIND0/3 calculations. lZo The p.e. spectra of various cyclopolyphosphines have been assigned with the aid of MIND0 calculations. 207

5 Diffraction X-Ray Diffraction.-Two PI1 compounds have been studied; the hydrochloride of the heterocycle (2; R=H)22 and the cation (59).208 The structures of PIr1

197

198

1 9 9

000

001

" 0 2

203

204

205

206

207

208

1 g 5 1. N. Zhniurova and V. G. Yurchenko, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 71

l 9 f i T. Klebach, C, Jongsma, and F. Bickelhaupt, R e d . Trau. Chim. Pays-Bas, 1979, 98, 14. (Chem. A h . , 1978, 88, 135 828).

E. A. Romanenko, S. V. Iskanova, and Yu. P. Egorov, Teor. Eksp. Khim., 1979, 15, 73 (Chem. Abs., 1979, 90, 186 204). G . V. Ratovskii, L. M. Sergienko, V. 1. Glukhikh, V. E. Kolbina, and N. A. Belykh, J. Gen. Chem. USSR (Engl. Transl.), 1978,48, 1817 (Chem. Abs., 1979,90,22 098). E. V. Megera and M. I. Shevchuk, J. Gen. Chem.USSR (Engl. Trans/.), 1978, 48, 1998 (Chent. Abs., 1979, 90, 55 032). V. V. Zverev and Yu. T. Kitaev, Russ. Chem. Rev. (Engl. Transl.), 1977, 46, 791. M. Mracec and Z. Simon, Rev. Roum. Chim., 1978, 23, 769. R. G. Cave11 and R. Sodhi, J. Electron Spectrosc. Relat. Phenom., 1979, 15, 145. L. W. Yarbrough and M. B. Hall, J. Chem. SOC., Chem. Commun., 1978, 161. V. V. Zverev and V. E. Bel'skii, Dolcl. Akad. Nauk SSSR, 1978, 241, 1367(Chem. Abs., 1978, 89, 196 810). G. Frenking, H. Goetz, and F. Marschner, J . Am. Cheni. Sot.., 1978, 100, 5295; M. J. S . Dewar, M. L. McKee, and H. S. Rzepa, ibid., p. 3607. A. Schweig, N. Thon, and H. Vermeer, J. E/ectron Spectrosc. Relat. Phenom., 1979, 15, 65. A. H. Cowley, M. J. S. Dewar, M. Lattman, J. L. Mills, and M. McKee, J . Am. Chein. SOC., 1978, 100, 3349. A. H. Cowley, M. C. Cushner, and J . S. Szobota, J. Am. CIiem. SOC., 1978, 100, 7784.

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264 Organophosphorus Chemistry

compounds which have been determined include the diphosphine (60), 209 a l-phospha-2,3-diazabicyclo[3.1.0]hexane,210 the tetraphosphine (61),211 a hexaphosphabicyclo [3.3.0]octane, 212 a 3,6-diphosphaoctanedicarboxylic acid,lss the phosphazane (62),213 a germaphosphacy~lohexane,~~~ and tris-m-tolyl- phosphine and its sulphide and selenide.216

In the PIV class, three cyclic phosphonium salts have been studied [a phos- phepin,21s the adamantane (63),la9$ 217 and the tetracyclo-octane (64) 218], two enol phosphonium salts, 219 and a carbodiphosphorane. 220 The PIV-N compounds

\ C0,Me

(60)

(59)

(64) (63)

2os’ H. J. Becher, W. Bensmann, D. Fenske, and B. Pfennig, Monatsh. Chem., 1978,109, 1023. 210 B. A. Arbuzov, V. D. Cherepinskii-Malov, E. N. Dianova, A. I. Gusev, and V. A. Sharapov,

211 R. E. Davis, C. W. Hudson, and E. P. Kyba, J . Am. Chem. Soc., 1978,100, 3642. 212 H. G. von Schnering and W. May, 2. Naturforsch., Teil B, 1978, 33, 698. 213 R. Keat, A. N. Keith, A. MacPhee, K. W. Muir, and D. G. Thompson, J. Chem. SOC.,

214 N. G. Bokii, A. I. Yanovskii, and Yu. T. Struchkov, Bull. Acad. Sci. USSR, Div. Chern.

21s T. S. Cameron, K. D. Howlett, and K. Miller, Acta Crystallogr., Sect. B, 1978, 34, 1639. 31G G. D. MacDonell, K. D. Berlin, S. E. Ealick, and D. van der Helm, Phosphorus Sulfur,

217 K. H. Jogun, J. J. Stezowski, E. Fluck, and H. Juergen, 2. Naturforsch., Teil B, 1978, 33,

218 M. Mazhar-ul-Haque Rashid and S. E. Cremer, J. Chem. Soc., Perkin Trans. 2, 1978, 1 1 15. 219 M. Yu. Antipin, A. E. Kalinin, Yu. T. Struchkov, I. M. Aladzheva,T. A. Mastyukova, and

M. I. Kabachnik, Zh. Strukt. Khirn., 1978,19,319 (Chem. Abs., 1978,89, 107 393); M. Yu. Antipin, T. N. Sal’nikova, A. E. Kalinin, Yu, T. Struchkov, I. M. Aladzheva, T. A. Mastryukova, and M. I. Kabachnik, ibid., p. 873 (Chem. Abs., 1979, 90, 121 724).

230 G. E. Hardy, 3. I. Zink, W. C. Kaska, and J. C. Baldwin,J. Am. Chem. Soc., 1978,100,8001.

Dokl. Akad. Nauk SSSR, 1978, 243, 358.

Cliem. Commun., 1978, 372.

Sci., 1978, 27, 328 (Chem. Abs., 1978, 88, 189 781).

1978, 4, 187.

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Physical Methods 265 studied include tri- and tetra-phosphazenes, 221 a bicyclic phosphazene,222 a tricyclic pho~phoramidate,~~~ a germyliminophosphorane, 224 a pyranose derivative, 226 NN-dimethylhydrazinotriphenylphosphonium bromide, 226 and a diazenyltriphenylphosphonium salt. 227 The crystal structures of the phosphine oxides (65), 26 (66),228 (67), 229 (68),230 and (69),231 of a tria~a-adarnantane,~~~ and of the two disulphides (70)232 and (71)233 have been established. In the phosphinyl class, di-t-pentylphosphinic acid,234 O-methylphenylphosphinyl- acetic acid,233” a hydroxycyclohexyl ph~sphinate ,~~~ and the heterocycles

221

‘“‘2

“23

2 2 4

‘Ph

(67)

/

(68 ) R = Ph

R. T. Oakley, N. L. Paddock, S. J. Rettig, and J. Trotter, Can. J. Chem., 1977, 55, 4206; H. P. Calhoun, R. T. Oakley, N. L. Paddock, S. J. Rettig, and J. Trotter, ibid., 1978, 56, 2833. T. S. Cameron, R. E. Cordes, and F. A. Jackman, Acta Crystallogr., Sect. B, 1979,35,980. F. Casabianca, F. A. Cotton, J. G. Riess, C. E. Rice, and B. R. Stults, Inorg. Chem., 1978, 17, 3232. W. S. Sheldrick, D. Schomburg, and W. Wolfsberger, 2. Naturforsch., Teil B, 1978, 33, 493.

L 1 3 K. B. Lindberg, A. Kalman, J. Kovacs, A. Messmer, and I. Pinter, Cryst. Struct. Commun.,

22b E. Stoeldt and R. Kreher, Chem. Ber., 1978, 111, 2037. 227 F. W. B. Einstein, D. Sutton, and P. L. Vogel, Can. J . Chem., 1978, 56, 891. “ L R E. Vilkas, M. Vilkas, D. Joniaux, and C. Pascard-Billy, J . Chem. Soc., Chem. Commun.,

’’N A. Fitzgerald, J. A. Campbell, G. D. Smith, C. N. Caughlan, and S. E. Cremer, J. Org.

330 W. Winter, Chem. Ber., 1978, 111, 2942. 231 M. L. Glowka, Acta Crystallogr., Sect. By 1978, 34, 3089. 232 J. Kaiser, R. Richter, and H. Hartung, Tetrahedron, 1978, 34, 1993. 233 J. D. Lee and A. H. Boloorizadeh, J. Organornet. Chem., 1978, 152, 305. 334 J. L. Solka, A. H. Reis, G. W. Mason, S. Lewey, and D. F. Peppard, J. Inorg. Nucl. Chem..

23h V. V. Tkachev, L. 0. Atovmyan, N. A. Kardanov, N. N. Godovikov, and M. I. Kabachnik,

1978, 7, 607.

1978, 125.

Chem., 1978, 43, 3513.

1978,40,663. Z. Galdecki and M. L. Glowka, Acta Crystallogr., Sect. B, 1978, 34, 2938.

Zh. Strukt. Khim., 1978, 19, 962 (Chem. Abs., 1979 90, 104074).

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266 Organophosphorus Chemistry

(72),237 (73),238 and (74) 239 have had their molecular structures determined; and with regard to phosphonyl compounds, reports have appeared on an cc-anilino-e~ter,~~~ an a-benzodioxole the chloro-amide (75),242 and the heterocycles (76),243 (77),244 and (78).245 The remaining PIV structures which have been studied are phosphoryl heterocycles, i.e. the phosphate (79),245 the sulphide (80),246 the selenide (81),247 the amides (82) 129 and (83),248 and a series of five-membered heterocycles based on the ring system (84).249 X-Ray diffraction

I Ph

(72)

S

OMe I I

(77)

OPh I

5 / I

Y

237 J. Jager, 2. Kristallogr., Kristallgeom., Kristallphys., Kristallchem., 1978, 147, 89. 2s8 T. M. Balthazor, J. A. Miles, and B. R. Stults, J. Org. Chem., 1978, 43, 4538. 239 G. Baccolini, E. Foresti, and A. Krajewski, J. Chem. Sor., Perkin Trans. 1, 1979, 893. 240 Z . Ruzii-Toros, B. Kojic-Prodic, and M. Sljukic, Acta Crystallogr., Sect. B, 1978,34, 31 10. 241 S. Kulpe and I. Seidel 2. Chem., 1978, 18, 221. 242 K. Paxton and T. A. Hamor, J. Chem. SOC., Dalton Trans., 1978, 647. 243 C. 0. Haagensen, Acta Crystallogr., Sect. B, 1978, 34, 3780. 244 J. P. Dutasta, A. Grand, and J. B. Robert, Acta Crystallogr., Sect. B, 1978, 34, 3820. 845 R. W. Warrent, C. N. Caughlan, J. H. Hargis, K. C. Yee, and W. G. Bentrude, J. Org.

246 J. Karolak-Wojciechowska, M. Wierzorek, A. Zwierzak, and S. Zawadzki, J. Chem. SOC.,

247 R. Kinas, W. J. Stec, and C. Krueger, Phosphorus Sulfur, 1978, 4, 295. 248 F. Ramirez, J. S. Ricci, J. F. Marecek, H. Okazaki, and M. Pike, J. Org. Chem., 1978,43,

4996. 249 R. Sarma, F. Ramirez, B. McKeever, M. Nowakowski, and J. F. Marecek, J. Am. Chem.

SOC., 1978,100,5391 ; M. W. Wieczorek, J. Karolak-Wojciechowska, M. Mikolajczyk, and M. Witczak, Acta Crystallogr., Sect. B, 1978,34,3138; M . W. Wieczorek, W. S. Sheldrick, J. Karolak-Wojciechowska, M. Mikolajczyk, and M. Witczak, Ibid., 1979, 35, 198; F. Ramirez, J. S. Ricci, H. Okazaki, K. Tasaka, and J. F. Marecek, J . Org. Chem., 1978,43, 3635

Chem., 1978,43,4266.

Perkin Trans. I , 1979, 146.

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Physical Methods 267

Ph \\ 0 (82)

( 8 3 )

Sihle, /

Me$ = N

(87)

studies of PV molecules 250 are mainly included in Chapter 2. The Pvl bipyridine- phosphate (85) has been found to have an octahedral Electron Diffraction.-There have been studies of the strained bicyclic phos- phite (86) 2 5 2 and of the silyliminophosphorane (87).253

6 Dipole Moments, Kerr Effect, and Polarography The Russian research schools continue to make extensive use of dipole moments and Kerr constants in conformational analysis, and the use of Kerr data in combination with other physical data has been reviewed.254 Such combinations have been used in the study of triarylphosphines, 255 trimethylsilyl derivatives of phosphites, phosphinates, and phosphates, 256 of arylpho~phonates,~~~ and of a number of I ,3,2-dioxa-phosphorinans 258 and -phospholans. 259 The polarity, 2io W. Schwarz, E. Fluck, and M. Vargas, Phosphorirs Sulfur, 1978, 5, 217; G. M. L. Cragg,

B. Davidowitz, G. V. Fazakerley, L. R. Nassimbeni, and R. J. Haines, J. Chem. SOC., Chem. Commun., 1978,510; S . Neumann, D. Schomburg, G. Richtarsky, and R. Schmutz- ler, ibid., p. 946; A. Schmidpeter, T. von Criegern, W. S. Sheldrick, and D. Schomburg, Tetrahedron Lett., 1978, 2857; H. Wunderlich, Acta Crystallogr., Sect. B, 1978, 34, 2015; V. A. Gilyarov, N. A. Tikhonina, V. G. Andrianov, Yu. T. Struchkov, and M. I. Kabach- nik, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 670 (Chem. Abs., 1978, 89, 109 181); W. Althoff, R. 0. Day, R. K. Brown, and R. R. Holmes, Inorg. Chem., 1978, 17, 3265; P. F. Meunier, R. 0. Day, J. R. Devillers, and R. R. Holmes, ibid. p. 3270; R. K. Brown, R. 0. Day, S. Husebye, and R. R. Holmes, ibid., p. 3276. W. S. Sheldrick, A. Schmidpeter, andT. von Criegern, Z. Naturforsch., Teil By 1978,33,583.

252 S . S. Shaidulin, V. A. Naumov, and N. A. Makarova, Zh. Strukt. Khim., 1978, 19, 942 (Chem. Abs., 1979,90, 121 548).

3L3 E. E. Astrup, A. M. Bouzga, and K. A. Starzewski, J. Mol. Struct., 1979, 51, 51. 254 R. P. Arshinova, Russ. Chem. Rev. (Engl. Transl.) 1977, 46, 809. 235 A. A. Shvets, Yu. I. Sukhorukov, S. B. Bulgarevich, and E. N. Tsvetkov, J. Gen. Chent.

USSR (Engl. Transl.), 1978, 48, 1986 (Chem. Abs., 1979, 90, 86 617). 226 0. A. Varnavskaya-Samarina, E. A. Ishmaeva, G. V. Romanov, R. Ya. Nazmutdinov,

A. B. Remizov, and A. N. Pudovik, Bull. Acad. Sci USSR, Div. Chem. Sci., 1978,27, 313 (Chem. Abs., 1978, 88, 189 908).

2 5 7 0. A. Varnavskaya, E. A. Ishmaeva, F. M. Kharrasova, A. B. Remizov, and A. N. Pudovik, Bull. Acad. Sci USSR, Dio. Chem. Sci., 1978, 27, 1603 (Chem. Abs., 1978, 89, 179 422).

358 R. P. Arshinova, V. E. Kataev, and B. A. Arbuzov, Bull. Acad. Sci. USSR, Diu. Chem. Sci., 1978, 27, 720 (Chem. Abs., 1978, 89, 23 653); B. A. Arbuzov, V. E. Kataev, R. P. Arshinova, and R. N. Gubaidullin, ibid., p. 2179 (Chem. Abs., 1979, 90, 86 624); E. A. Ishmaeva, 1. I. Patsanovskii, M. Mikolajczyk, B. Ziemnicka, J. Krzywanski, and A. N. Pudovik, Dokl. Akad. Nauk SSSR, 1978,242, 620 (Chem. Abs., 1979,90, 5757).

269 R. P. Arshinova, E. T. Mukmenev, L. I. Gurarii, and B. A. Arbuzov, Bull. Acad. Sci. USSR, Diu. Chem. Sci., 1978, 27, 524 (Chem. Abs., 1978, 89, 42 221).

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268 Organophosphorus Chemistry

polarizability, and conformations of PII1 cyanides have been studied,260 and the influence of unsaturation and conjugation on the polarity of PIv compounds has been reviewed.2s1 There has also been a recent study of the polarity and polarizability of acetylenic compounds.262 A study of the Kerr effect of triaryl- phosphine sulphides indicated that meta- and para-orientated Me and C1 groups do not alter the conformational preferences of the aryl rings.263 A study of the dipole moments of a range of selenides showed that the P-Se group makes a larger contribution to the overall moment than do P=O or P=S groups,264 and a study of ylides indicated that Ph3P=CH2 has 55% ionic character.265 Dipole-moment data support a boat conformation for the phosphines (88 ; R= Me, Et, or Pri).266 Other reports on polarizabilities have centred on phos- phinates, 267 cyclic phosphonates,268 complexes of phosphoryl compounds with alcohols and phenols,2sg and a cyclotriphosphazene. 270 The cis-trans geometry of some P-alkoxyvinyl-phosphonates was estimated by measuring dipole

Polarographic and Related Studies.-Polarographic studies have been reported on the reduction of nitrophenophosphazines, 272 the adsorption of phosphinates by mercury electrodes, 273 the oxidation of semicarbazido-pho~phonates,~~~ the structure of a pho~phoramidate,~~~ and the interference effects of phosphine

E. A. Ishmaeva, I. I. Patsanovskii, W. J. Stec, B. Uznanski, and A. N. Pudovik, Dokl. Akad. Nauk SSSR, 1978,240, 1361 (Chem. Abs., 1978, 89 162 928).

zG1 E. A. Ishmaeva, Russ. Chem. Rev. (Engl. Transl.), 1978, 47, 896. 362 E. A. Ishmaeva, A. N. Vereshchagin, N. G. Khusainova, 2. A. Bredikhina, and A. N.

Pudovik, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978, 27, 310 (Chem. Abs., 1978, 88, 169 498).

3G3 S. B. Bulgarevich, L. V. Concharova, 0. A. Osipov, V. V. Kesarev, and A. A. Shvet, J . Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1219.

264 R. R. Shagidullin, I. I. Vandyukova, and 1. A. Nuretdinov, Bull. Acad. Sci USSR, Dic.. Chem. Sci., 1978, 27, 1225.

2G5 H. Lumbroso, J. Cure, and H. J. Bestmann, J. Organomet. Chem., 1978, 161, 347. 2GG 0. A. Varnavskaya, E. A. Ishmaeva, V. M. D'yakov, and N. M. Kudyakov, Bull. Acad.

3G7 S. Kh. Nurtdinov, V. F. Novikov, and N. M. Ismagilova, Chem. Abs., 1978, 89, 162 91 1 . 268 E. A. Ishmaeva, V. V. Ovchinnikov, and A. N. Pudovik, Bull. Acad. Sci. USSR, Div.

Chem. Sci., 1978,27, 1911 (Chem. Abs., 1979,90,22 188). 2G9 E. I. Matrosov, G. M. Petov, and M. I. Kabachnik, Bull. Acad. Sci. USSR, Diu. Chem. Sci.,

1978,27,2025 (Chem. Abs., 1979,90, 120 763). 270 V. G. Devendyaeva, Y. V. Kolodyazhnyi, S. G. Fedorov, S. K. Alieva, S. F. Zapuskalova,

S. G. Gol'din, and 0. A. Osipov, J. Gen. Chem. USSR (Engl. Transl.), 1977, 47, 2286. 371 G. A. Kutyrev, N. V. Kashina, E. A. Ishmaeva, R. A. Cherkasov, and A. N. Pudovik,

J. Gen. Chem. USSR (Engl. Transl.), 1977,47,2249 (Chem Abs., 1978,88,88 727). z 7 2 M. K. Polievktov, A. I. Bokanov, 0. G. Piskunova, and B. 1. Stepanov, J. Gen. Chcm.

USSR (Engl. Transl.), 1977, 47, 2486 (Chem. Abs., 1978, 88, 104 395). 2 7 3 H.-D. Doerfler, Colloid Polym. Sci., 1978, 256, 798. 274 L. K. Trentovskaya, G. S. Supin, N. N. Mel'nikov, 0. B. Mikhailova, and A. F. Grapov,

J. Gen. Chem. USSR (Engl. Transl.), 1977,47, 2424 (Chem. Abs., 1978, 88, 105 471). 2 7 5 V. M. Ovrutskii, L. D. Protsenko, L. G . Sachenko, and N. D. Denisov, J. Gen. Chem.

USSR (Engl. Transl.), 1977, 47, 2294.

Sci. USSR, Div. Chem. Sci., 1978,27, 1880 (Chem. Abs., 1979,90,22 187).

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Physical Methods 269

oxides 376 and phosphonium There have also been some biochemical applications ; 278 e.g., pyridoxal 5'-phosphate. Relationships between electro- kinetic potential and surface activity have been studied, using vinylphosphonium

7 Mass Spectrometry The field ionization mass spectra of a series of phosphites 280 and phosphonates 281

have been studied. The electron-impact-induced fragmentations of the following compounds have been reported : ortho-substituted-aryl-phosphines and -phos- phinic and -phosphonic acids, 282 trityl- and triarylsilyl-iminophosphoranes, 283 four-, five-, and six-membered cyclic phosphine oxides,284 a series of alkyl phosphonyl dichlorides 285 and alkanephosphonates, 286 dithio- and thio- phosphonic anhydrides, 287 and dibenzodiazaphosphepines. 288 There has been further work on the use of mass spectrometry to distinguish isomers. The spectra of diastereoisomeric 1,3,2-dioxaphosphorinans differed only in the intensities of certain ions,289 whereas the isomeric A2- and A3-phospholen oxides (89) gave, as their second most abundant ions, peaks corresponding to (M-Ph)+ and C5Hs+, respectively. 290

The dithiophosphonate derivatives of peptides give ions related to the sequence as well as to the nature of the C-terminal a r n i n o - a ~ i d . ~ ~ ~ The trifluoroacetates

3 i 6 E. Mueller and H.-D. Doerfler, J. Electroanal. Clrem. Interfacial Electrochem., 1979, 99,

277 Yu. V. Mikhailik and B. B. Damaskin, Elektroltlzimiya, 1979, 15, 566. 2 7 8 J. Llor, E. Lopez-Cantarero, and M. Cortijo, Bioelectrochem. Bioenerg., 1978,5, 276; M.

P. Colleoni and R. Grazzini, Riu. Farmacol. Tcr., 1977, 8, 185; J. Llor and M. Cortijo, J. Chem. SOC., Perkin Trans. 2 , 1978, 409.

279 M. 1. Shevchuk, I. V. Megera, V. P. Rudi, and M. A. Kirmaev, Zh. Obshch. Khim., 1978, 48, 324 (Chem. Abs., 1978, 89, 31 205); M. I. Shevchuk, I. V. Megera, V. P. Rudi, and M. A. Kirmaev, J. Gen. Chem. USSR (Engl. Transl.), 1978, 47, 290.

2R0 V. B. Labintsev, N. N. Grishin, and A. A. Petrov, Zh. Org. Khim., 1978, 14, 1134 (Chem. Abs., 1978,89,89 822); V. B. Labintsev, Yu. K. Gusev, N. N. Grishin V. N. Chistokletov, and A. A. Petrov, ibid., p. 1138 (Chem. Abs., 1978, 89, 89 823).

281 V. B. Labintsev, Yu. K. Gusev, N. N. Grishin, and A. A. Petrov, Zh. Org. Khim., 1978,14, 1371 (Chem. Abs., 1979,90, 5420).

3 8 2 R. V. Poponova, E. N. Dolzhnikova, E. N. Tsvetkov, and G. S. Petrova, J. Gen. Chem. USSR (Engl. Trartsl.), 1978, 48, 1782 (Chem. Abs., 1979, 90, 5452).

383 S. Yolles, M. F. Sartori, and J. H. Woodland, J. Chem. Eng. Data, 1978, 23, 260. 284 C. W. Koch, D. H. Eargle, and G. L. Kenyon, Org. Mass Spectrom., 1977, 12, 624. 285 W. R. Griffiths and J. C. Tebby, Phosphorus Sulfiir, 1978, 4, 341. 286 W. R. Griffiths and J. C. Tebby, Phosphorits Sulfur, 1978, 5, 101.

288 M. S. R. Naidu and C. D. Reddy, Bull. Chem. SOC. Jpn., 1978, 51, 2156. 289 B. Zielinska and W. J. Stec, Org. Mass Spectrom., 1978, 13, 65. 290 K. Moedritzer and R. E. Miller, Synth. React. Inorg. Metal-Org. Chem., 1978, 8, 167. 291 V. F. Sizoi, G. Nurgalieva, Y. S. Nekrasov, A. E. Shipov, M. S. Vaisberg, T. A. Mastryu-

kova, amd M. I. Kabachnik, Bull. Acod. Sci. USSR, Div. Chem. Sci., 1978, 27, 987.

1 1 1 .

H. Keck and W. Kuchen, Phosphorus Sulfur, 1978,4, 173.

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270 Organophosphorus Chemistry

are stable derivatives of aminophosphonic acids and are suitable for g.c.-mass spectroscopic analysis.292 Dimethyl 2-0~0(7-~H~)heptylphosphonate has been prepared, for use as a standard in the assay of prostaglandins and thromboxane. 293

Dimethylthiophosphinate derivatives of phenols have been studied, and recom- mended for g.c.-m.s. analysis of acidic catecholamine metabolites. 294 The estimation of cyclophosphamide by g.c. plus chemical ionization mass spectro- metry has been described. 295 The absolute configurations of 170,180-labelled phosphate esters have been determined from metastable ions (limited-scan method) due to the elimination of formaldehyde from the P-methoxy-groups. 296

Negative-ion spectra of phosphoryl and thiophosphoryl compounds have been described, 297 and the collision-activation spectra of phosphonium salts produced by field desorption have been interpreted. 298 Ion cyclotron resonance spectroscopy has been applied to trimethylphosphonium ylides and imino- phosphorane~,~~~ and to the amino-fluoro-phosphine Me2NPF2. 300

8 pKa and Thermochemical Studies The acidities of protonated phosphines in dimethyl sulphoxide have been studied and an absolute pH scale (pH 11-28) has been tentatively established.301 The dissociation constants of d i a r ~ l - ~ ~ ~ and dialk~l-~O~ phosphinic acids, in various media, have been determined. The acid strengths of phosphinic or phosphonic acids and carboxylic acids in water or aqueous alcohol have been related.304 The equilibrium constants involving the formation of HA 2- com- plexes from phosphorus acids (HA) are largest for dibasic The pKa

2 y 2 J. W. Huber, J. Chromatogr., 1978, 152, 220. 293 D. F. Taber and C. H. Lee, J. Labelled Compd, Radiopharm., 1978, 14, 599. 294 K. Jacob, E. Maier, G. Schwertfeger, W. Vogt, and M. Knedel, Biomed. Mass Spectrom.,

1978, 5, 302. 295 I. Jardine, C. Fenselau, M. Appler, and M. N. Kan, Stable hot . , Proc. Internat. Symp.,

1977, 1978, 97. 296 S. J. Abbott, S. R. Jones, S. A. Weinman, and J. R. Knowles, J. Am. Cliem. SOC., 1978,

100,2558. 297 H. J. Meyer, F. C. V. Larsson, S. 0. Lawesson, and D. H. Bowie, Bull. SOC. Chim. Belg.,

1978, 87, 517. 29H H. J. Veith, Org. Mass Spcctrom., 1978, 13, 280; R. Weber, F. Borchers, K. Levsen, and

F. W. Roellgen, 2. Naturforsch., Teil A , 1978, 33, 540. 299 0. R. Hartmann, K. P. Wanczek and H. Hartmann, Dyn. Mass Spectrom., 1978, 5, 146;

0. R. Hartmann, K. P. Wanczek, and H. Hartmann, Lect. Notes Chem., 1978, No. 7 , Ion Cyclotron Reson. Spectrom., p. 283; 0. R. Hartmann, K. P. Wanczek, and H. Hartmann, Ado. Mass Spectrom., Sect. A, 1978, 7, 274.

300 K. P. Wanczek, H. Hartmann, and G. V. Roeschenthaler, Adv. Mass Spectrom., Sect. B, 1978, 7, 1301.

301 J. Chrisment, D. Nicole, and J. J. Delpuech, C. R. Hebd. Seances Acad. Sci., Ser. C , 1978, 286, 541 ; J. J. Delpuech and D. Nicole, J. Chem. Res. (S) , 1978, 208.

302 A. A. Kryuchkov, A. G. Kozachenko, E. I. Matrosov, and M. I. Kabachnik, Bull. Acad. Sci. USSR, Diu. Chem. Sci., 1978, 27, 1746.

303 0. G. Piskunova, L. A. Yagodina, B. A. Korolev, A. 1. Bokanov, and B. I. Stepanov, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1205.

304 B. I. Istomin and V. A. Baranskii, Org. React (Tartu), 1978, 15, 222; V. A. Baranskii and B. I. Istomin, ibid., p. 230; B. I. Istomin, V. A. Baranskii, and A. V. Kalabina, ibid., p. 275. V. P. Barabanov, A. Ya. Tret’yakova, and F. M. Kharrasova, J. Gen. Chem. USSR (Engl. Transl.), 1978 48, 1391.

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Physical Methods 271

values of various amino-phosphonic acids 306 and phosphorous acids 9 30g

have been measured, and in the latter study these have been related to wonstants. 308 The electronic properties of phosphonium and phosphinyl groups have been estimated from the pKa values of the substituted benzoic acids. The calculated Hammett a-constants were: R3P+, 0.86-0.98 ; R,P(O), 0.32-0.45; R,P(S), 0.31 ; and (R,N),P(O), 0.21.309

Reports have also appeared on the basicities of P-carbonyl compounds and the acid-base properties of the enol forms of some p h o ~ p h o n a t e s . ~ ~ ~

The pKa data of mono- and di-(4-octylphenyl)phosphonic acids have been presented and discussed in terms of their use in PVC calcium-ion-selective electrodes. 312

0 0

K',PCH ,CK2

(90)

I ! I1

Two thermochemical studies have been reported, one on the heats of formation of triphenylph~sphine,~~~ the other on the heats of solution of the complex of tributyl phosphate and nitric acid.314 There have also been d.t.a. studies of the reactions between CC14 and RP(OPh), 316 and Y,PCI and E ~ O C H M ~ O A C . ~ ~ ~

9 Chromatography The partition data on 0-alkyl 0-aryl phenylphosphonates show that g.1.c. behaviour is determined mainly by electronic and steric forces, whereas the t.1.c. behaviour is determined by electronic and hydrophobic forces that depend on the polarity of the mobile phase.317

30G D. Redmore, J . Org. Chem., 1978,43, 996; H. Gross, T. Ya. Medved', B. Costisella, F. I. Bel'skii, and M. I. Kabachnik, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 1746.

307 V. V. Ovchinnikov, 0. A. Cherkasova, E. G. Yarkova, N. A. Mukmeneva, A. N. Pudovik, and R. A. Cherkasov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1978,27,595 (Chem. Abs., 1978, 89, 107 593); J. P. Guthrie, Can. J. Chem., 1979, 57, 236.

308 E. N. Tsvetkov, M. I. Terekhova, E. S . Petrov, R. A. Malevannaya, S. P. Mesyats, A. I. Shatenshtein, and M. I. Kabachnik, Bull. Acad. Sci. USSR, Diu. Chem. Sci., 1978, 27, 1743 (Chem. Abs., 1979,90, 38 411).

309 E. N. Tsvetkov, I. G. Malakhova, and M. I. Kabachnik, J. Gen. Chem. USSR (Engi. Transl.), 1978, 48, 1125 (Chem. Abs., 1978, 89, 107 696).

310 N. K. Skvortsov and B. I. Ionin, J. Gen. Chem. USSR (Engl. Transl.), 1978,48,708 (Chcm. Abs., 1978, 89, 42 163).

311 0. Yu. Timofeeva, A. V. Fuzhenkova, T. D. Sorokina, and G. K. Moiseeva, Deposited Document, 1976, VINITI 2722 (Chem. Abs., 1979,90, 71 554).

312 A. Craggs, P. G. Delduca, L. Keil, B. J. Key, G. J. Moody, and J. D. R. Thomas, J. Inorg. Nucl. Chem., 1978, 40, 1483.

313 W. V. Steele, J. Chem. Thermodyn., 1979, 11, 187. 314 A. I. Zarubin, E. A. Kanevskii, and M. V. Belov, J . Gen. Chem. USSR (Engl. Transl.),

1978,48, 1536. 315 F. M. Kharrasova, V. D. Efimova, M. M. Eremina, and R. A. Salakhutdinov, J. Gen.

Chem. USSR (Engl. Transl.), 1978 48, 948 (Chem. Abs., 1978, 89, 59 941). 316 M. B. Gazizov, T. V. Zykova, N. P. Anoshina, D. B. Sultanova, and R. A. Salakhutdinov,

J . Gen. Chem, USSR (Engl. Transl.), 1978,48, 1802 (Chem. Abs., 1978, 89, 214 607). 317 W. Steurbaut, W. Dejonckheere, and R. H. Kips, J . Chromatogr., 1978, 160, 37.

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272 Organophosphorus Chemistry

G.1.c.-Reports have concerned the analysis of various phosphorochloridates,318 phosphoramidothioates,319 cyclophosphamide, 320 and various pesticides. 321 T.1.c.-Ninhydrin has been recommended for developing chromatograms of PI1

T.1.c. separations have been described for various phosphorus steroid and sugar phosphates,324 condensed phosphates, 325

d i m e t h ~ a t e , ~ ~ ~ and various biochemically important Paper Chromatography.-A study of phosphine oxides, phosphinates, phos- phonates, and phosphates by reversed-phase chromatography on acetylated paper showed that the RF values were related to the number of carbon The factors influencing the analysis of technetium-99-labelled phosphorus compounds have been discussed. 329

Column Chromatography.-The liquid-liquid partition coefficients of trioctyl- phosphine oxide have been related to solubility parameters. 330 The adsorption energies of nucleoside polyphosphates on hydroxyapatite columns have been determined. 331

31R 0. A. Vselyubskaya, I. I. Kolodkina, A. M. Yarkovich, and M. T. S. Yanotovskii, Khim.- Farm. Zh., 1979, 13, 106 (Chem. Abs., 1979, 90, 179 667).

319 N. Oi, H. Shimada, 0. Hiroaki, M. Horiba, and H. Kitahara, Bunseki Kagaku, 1979, 28, 64.

320 B. Whitting, S. M. K. Miller, and €5. Caddy, Br. J. Clin. Plaarmacol., 1978, 6, 373; T. Facchinetti, M. D’Incalci, M. Giampiers, L. Cantoni, G. Belvedere, and M. Salmona, J. Chromatogr., 1978, 145, 315.

3 2 1 A. Katona, F. Kulcsar, and T. V. Komives, Elelmiszervizsgalati Kozl., 1977, 23, 178 (Chem. Abs., 1978,89, 74 293); T. Ishida, M. Imanaka, and K. Matsunaga, Okayama-Ken Kankyo Hoken Senta Nempo, 1977,l. 208 (Chem. Abs., 1978,89, 88 897); A. Vioque and T. Albi, Grams Aceites (Seville), 1978,29,37 (Chem. Abs., 1978,89,145 161); P. Lombard0 and I. J. Egry, J. Assoc. Of? Analyt. Chem., 1979, 62, 47.

323 D. A. Prodvoditelev, V. 1. Ivanov, Kh. Kh. Alarkon, and E. E. Nifant’ev, J. Gen. Chern. USSR (Engl. Trans/.), 1978, 48, 1165.

323 I. V. Komlev, P. P. Dakhnov, and L. M. Troitskaya, Z?i. Anal. Khim., 1978, 33, 2046 (Chem. Abs., 1979, 90, 80 396).

324 T. 0. Kumara, Bunseki Kagaku, 1978, 27, 793 (Chem. A h . , 1979, 90, 132 335). 3 2 5 E.A.Prodan and I. L. Shashkova, Vestsi Akad. Navuk B. SSR, Ser. Khim. Navuk, 1978,479

(Chem. Abs., 1978, 89, 178 616). 3 2 G T. Komives and A. Katona, Elelmiszeraizsgalati Kozl., 1977,23,244 (Chem. Abs., 1978,89,

213 667). 327 J. S. Miller and R. R. Burgess, Biochemistry, 1978, 17,2054, 2059; B. K. Kudelin, Yu. L.

Kaminskii, and I. F. Ivanova, Nov. Khim. Nukleozidov Nukleotidou, 1978,46 (Chem. Abs., 1979, 90, 55230); B. K. Kudelin, Yu. L. Kaminskii, and 1. F. Ivanova, Biokhimiya (Moscow), 1979, 44, 368 (Chem. Abs., 1979, 90, 164 145); A. Martin-Ponthieu and N. Porchet, Clin. Chem. ( Winston-Salem, N.C.), 1979, 25, 31 ; R. Schmidt, D. Kunze, and E. Egger, 2. Med. Laboratoriumsdiagn., 1978, 19, 306; C. Michalec and J. Reinisova. J. Chromatogr., 1979, 162,229.

328 C. Y. Yuen, W. C. Ye, and H. C. Pao, Hua Hsireh Hsueh Pao, 1978, 36, 113 (Chem. Abs., 1978, 89, 156 950).

329 A. Owunwanne, D. A. Weber, and R. E. O’Mara, J. N d . Med., 1978, 19, 534. 330 K. Akiba andT. Sugano, Kakuriken Kenkyu K o k o h (Tohoko Daigakii), 1976,9,272 (Chem.

331 T. Kawasaki, J. Chromatogr., 1978, 151, 95. Abs., 1979, 90, 167 805).

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