tmc literature highlights — 3

118 TMC literature highlights - 3 Transition Met. Chem. 10, 118-120 (1985)

Acknowledgements

We wish to express our gratitude to Drs. I. R. Girling and D. W. Young and Drs. J. E. and N. Turp for their invaluable advice, and to Basrah University for granting academic leave to one of us (Y.Z.Y.).

References

0) K. Tokuda, H. Daifuku, K. Aoki and H. Matsuda, Recent Advances in the Electrochemistry of Energy Generation, Storage and Conversion, National Science Foundation, Washington/Japan Society for Promotion of Science, Tokyo, Joint Seminar, Honolulu, Hawaii, May 1982, p. 71. - (2) R. Memming and F. Schroppel, Chem. Phys. Lett., 62, 207 (1979); R, Memming, Surf. Sci., 101, 551 (1980).- (3) K. Davies, A. Hamnett, K. R. Seddon and Y. Z. Yousif, unpublished results. - (4) C. G. Gfiggs and D. J. H. Smith, J. Chem. Soc., Perkin Trans. I, 3041 (1982). - (5) T. Sato, R. Nishida, Y. Kuwahara, H.

Fukami and S. Ishii, Agr. Biol. Chem., 40, 395 (1976). - (6) A. V. Rama Rao, M. N. Deshmukh and M. Kamalam, Tetrahedron, 37, 227 (1981). - (7)W. Bleyberg and H. Ulrich, Chem. Ber., 64B, 2504 (1931); F. Collins, Proc. Roy. Soc. (London), 158A, 696 (1937); H. A. Schuette, R. M. Christenson and H. A. Vogel, Oil and Soap, 20, 263 (1943). - (8) G. M. Robinson, J. Chem. Soc., 1543 (1934). - (9) R. G. Jones, J. Am. Chem. Soc., 69, 2350 (1947). - 00) H. Oura, J. Hase, K. Honda and S. Fukai, J. Pharm. Soc. Japan, 76, 1433 (1956) [Chem. Abstr., 51, 6515e (1957)].

0a) D. E. Ames, R. E. Bowman and R. G. Mason, J. Chem. Soc., 174 (1950). - (12) A. Watanabe, Bull. Chem. Soc. Japan, 34, 398 (1961). - (13) S. K. Ries, V. Wcrt, C. C. Sweely and R. A. Leavitt, Science, 195, 1339 (1977); S. K. Ries and W. Violet, Planta, 135, 77 (1977).- (~4) A. C. Chibnall, E. F. Williams, A. L. Latner and S. H. Piper, Biochem. J., 27, 1885 (1933).

Received January 18th, 1985) TMC 1292(C)

TMC Literature Highlights- 3*

Organometallic chemistry

Extraordinarily high selectivity has been observed (z) in nucleophilic addition to two isomers of [Mo(~S-CsH5) - (CO) (NO) (~13-cyclooctenyl)] +. The isomers differ in the orien- tation of the ~3-CsH13 ring relative to the cyclopentadienyl group. The system is described as exo when the methylene groups of the C8 ring are distal to the cyclopentadienyl ring, and endo when they are proximal. Deuteride addition to the exo isomer of the cyclooctenyl cation gives >99% (RR, SS) [Mo(vlS-Cp)(CO)(NO)(~12-CsH13D)] whereas the endo isomer affords ca. 95% of the (RS, SR) product. High regioselectivity for the addition of OH- , S2CNMe~ and dime- thylmalonate to the exo isomer was also observed. However, regioselectivity of nucleophilic addition to the endo isomer varies with the type of nucleophile and the reaction conditions. The results were rationalised by consideration of the intercon- version rates of the two cations (exo ,~ endo) and the interme- diate produced in the reactions. The formation of the nucleophile-C bond is apparently directed by the NO group and occurs cis to the NO group in both the exo and endo isomers.

Reaction of [TiC13(THF)3] with PhC2Ph and i-PrMgC1 in THF gives (2) an anionic cyclobutadiene complex, [Mg2C13- (THF)6][Ti(~14-C4Ph4)C13]. The structure of the anion was established crystallographically. Atoms of rhenium reacted with benzene and alkanes giving [QI6-C6H6)Re(II-R )- (~I-H)2Re016-C6H6)]([x-R = CHMe, CHEt, CMe2, etc.) (3). Mn or Re atoms co-condensed with benzene and PMe3 affording [Mn(@-C6H6)(PMe3)2H] or [(Re(@-C6H6)(PMe3)2}2] (4). The latter was reduced by K film in THF, and on treatment with MeI (which gave an iodide) followed by LiA1H4, [Re(~l 6- C6H6)(PMe3)2H] was formed.

Protonation of [Co(@-CsMes)(~12-C2H4)(PR3)] (R = Me, Ph (5) 5 + 1 23 orp-tolyl) gives [Co01 -CsMes)(PR3)Et] . H a n d C n.m.r.

spectral studies and an x-ray crystallographic study of the

* TMC Literature Highlights - 2: Transition Met. Chem., 10, 31 (1985)

0340-4285/85/0303-0118502.50/0

cation containing P(C6H4Me-p)3 (as a BF2 salt and PhMe solvate) established that there is a strong three-centre interaction between the metal and the ~-C hydrogen atom. [Ir2015- C5Me5)2C14] reacts with A12Me6 in n-pentane to give (6) [{Ir01L CsMes)Me3}2A1Me]. This reacts further with PPh3 or C2H4 (L) affording [Ir(~5-CsMe5)LMes], with Me2CO to give [{Ir(~l L CsMes)Me2}2(bt-CH2)2] , and With 02 in air to giv e the Ir v alkyl complex, [Ir(@-CsMes)Me4].

Reactions of coordinated ligands

Reaction of [Fe01LCp) (dppe) (CO)]PF6 (dppe = Ph2PCH2CH2PPh2) with BH4 in THF/CH2C12 at -78 ~ gives [Fe(nLCp)(dppe)(CO)H ] , via [Fe(~lS-Cp) (dppe) (CHO)] which was detected at low temperature. This carbonyl hydride reacts with LiA1H4 in refluxing THF/CH2C12 mixtures affording [Fe(n4-CsU6)(dppe)(CO)] and [Fe(~lS-Cp)(dppe)Me]. [Fe01LCp)(dppe)(CO)H] disproportionates in THF into [Fe(~lLCp)(d~pe)Me ] and [Fe01LCp)(dppe)(CHO)]. Anionic formyl and ~l -MeCHO complexes are formed by addition of LiBHEt3 to [Mo(~IS-Cp)(CO)3Me] (8). Thus, in the -78 to -60~ temperature range, [Mo01LCp)(CO)2Me(CHO)] - is formed, and on gradual warming, first to 20~ and then to room temperature, [Mo01LCp)(CO)2H(COMe)]- and Mo(~ISCp)(CO)2(~12-MeCHO)] -, respectively, are produced.

Addition of HBF4, CF3SO3H or CF3CO2H to [W{HB(pyz)3}(CO)2(--CSMe)] (pyz = pyrazolyl) affords (9) [W{HB(pyz)3}(CO)2(~I2-CHSMe)] whose x-ray structure determination confirmed the dihapto-carbene bonding.

Organolanthanide chemistry

Reaction of MI2 (M = Eu or Yb) with NaN(SiMe3)2 in dimethoxyethane gives (1~ the salt Na[M{N(SiMe3)}3]. If the reaction is carried out in the presence of Et20, then [Yb{N(SiMe3)2}(OEt2)2] is formed. Structures were deter-

�9 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1985

Transition Met. Chem. 10, 118-120 (1985) TMC literature highlights- 3 119

mined crystallographically and it was established that the lan- thanide atom was bound to one N(SiMe3)2 group exclusively, but shared the other two with Na § ions.

The x-ray structural examination of Sm01LCeMee)2, obtained (u) by desolvation of the bis-THF solvate at 75 ~ revealed that the rings are tilted with respect to 'each other, giving the molecule an "oyster"-like shape.

Coordination chemistry

Treatment of Cu(NO3)e with 1,4,7-triazacyclododecane (TCD) in MeOH affords (a2) [Cu(TCD)(NO3)]NO3. This Cu H species shows a quasi-reversible one-electron oxidation Wave, detected by cyclic voltammetry in MeCN, at -185 mV versus the [Fe01e-Cp)~]/[Fe(~ILCp)2] + couple, in contrast to the beha- viour of [Cu(dien)] z+ (dien = diethylenetriamine), which exhibits an irreversible wave at Ep = -450 mY. Optical and e.s.r, spectral studies reveal that [Cu(dien)] 2+ binds one CN- strongly in an equatorial plane, whereas [Cu(TCD)] z+ coordi- nates two CN- ligands, with possible de-coordination or sub- stantial bond weakening of one of the N donor atoms of the TCD ligand. X-ray structural examination of [Cu(TCD)- (NO3)]NO3 shows an irregular trigonal bipyramidal structure for the cation, with the axial positions occupied by one O atom of bidentate NO 3 and the central N atom of the TCD ligand.

The presence of a bridging hydrazido(3-)-ligand* was established (13) (Figure 1) in an x-ray crystallographic examination of the product obtained by treatment of [Mo{N2C- (S)(SEt)}{NH2NC(S)(SEt)}(S2CNEt2)2] with conc, HC1 in MeOH.

Treatment of [{Mo(CH2Ph)(NMe2)2}2] with i-PrOH gives (14) [{Mo(CH2Ph)(OPr-i)2}2]. Addition to this of PMe~ affords [(PfO)3MoMo(CHzPh)2(OPr-i)(PMe3)] and crystallographic studies of this showed that one Mo atom has a trigonal arrangement of ligands whereas the other has a square planar disposition. 1H n.m.r, spectral studies reveal a temperature- dependent equilibrium between this unsymmetrical species, [(i-PrO)2(PhCH2)Mo=Mo(CHzPh)(OPr-i)2], and free PMe3.

The [W2CI4(~t-OR)2(ROH)2] (R = Et or Pr) complexes pro- mote (e) reductive coupling of R'R"CO to give [W2CI4(~t- OR)z{R'R"C(O)C(O)R'R"}z] (Figure 2) or {W2C14(p~-OEt)2 {MePrC(O)C(O)MePr}], depending on the choice of ketone.

SEt /

N~C 0 / \

L2J.N ~ ~ . ~ _ _ _ _ I V I O .~, Iv I N ~ 1[ 2

S / "-N / NS'~. S Z \ 1 N~ C

k SEt

Figure 1. Complex containing a hydrazido(3-) ligand*.

The role of the dimetal unit is to provide electrons for the reduction of the ketones and to serve as the template for the coupling of the resulting ketyl radicals.

~ ' . . . \ / / a ' o/C ~ C"- 0

C l ~ ~ 9 ~ \_ ~c1

o g o / o

R" R" Figure 2. Structure of W2C14([I-OR)2 {R'R"C(O)C(O)R'R"}2.

Nitrosyl complexes

Nitric oxide reacts with [{Ru01LCp)(CO)2}2] at 170~ to give air-stable [Ru(~(-Cp)(~t-NO)}a] which contains (16) a Ru=Ru bond, Treatment of this compound with N2CHR (R = H or Et) gives [{Ru(~lS-Cp)(NO)2}2(~t-CHR)].

OsC13 reacts with $3N3C13 giving (17) Os(NS)C13, and addition to this of Ph4PC1 in aqueous solution, followed by recrys- tallisation from aqueous MeOH, affords first [Ph4P]z- [Os(NS)Cle] and then [Ph4P][Os(NS)C14(H20)]. An x-ray crystallographic examination of the latter revealed an almost linear Os-N-S system with HeO trans to the thionitrosyl group.

Treatment of [HRu3(CO)n]- with NOBF4 in moist MeCN gives (as) [Ru3(CO)la], [HRu3(CO)10(NO)], [HRu3(CO)10- (NHz)] and [HRu4N(CO)12]. Direct hydrogenation of [HRu3(CO)10(NO)] at 1 arm. and 100~ affords [HRu3(CO)w(NHz)], [HRu4N(CO)lz] [HeRu4(CO)12], "and [H2Ru3(CO)9NH]. Reaction of [Ost0C(CO)24] 2- with NOBF4 in MeCN produces [Os10C(CO)24(P,2-NO)]- in which the NO ligand adopts (19) a novel binding mode, bridging the wing-tips of a butterfly indentation of the Os atoms. Rearrangement, with CO loss, in solution gives [OsloC(CO)23(NO)]- whose geometry is similar to that of [Os10C(CO)24] 2- with the NO group bonded terminally to an Os atom in the tetrahedral Osa0 metal skeleton.

Clusters

Reaction of [{Mo(~le-(CeMes)(CO)2}2] with As4S 4 at 100 ~ gives (2~ the three compounds shown in Figure 3 in low yield.

As_ ~ As

(co)~ (cob ""X

, s / S \ A s

"<

Mo(CO)2

Figure 3. Structure of Mo2(~I-CeMee)z(CO)4As2, Mo2(rI-Cp)2AszS3 and Mo (TI-CsMee) (CO)2As3.

In a search to establish the existence of U-U bonds, the structures of [U30(OBu-t)20] and [U2(OPr-i)10] have been determined (21). In the former the three metals form a triangu- lar unit similar to that in [Mo30(OCH2Bu-t)m], with U-U distances of 3.58 A. In the latter, where there are two ~t-OPr-i groups, the metal-metal distance is 3.79 A. In neither of these species does a metal-metal bond exist and it was suggested that in U TM and U v systems there is only a faint possibility of finding such an interaction, although it might occur in U m complexes,

Reaction of [Rh(t-Bu3P)2HC1] with [Rh(CO)(t-Bu3P)2C1] and diborane in benzene gives (22) [Rhss(t-Bu3P)12C120]. The number 55 is one of the magic numbers of a full-shell cubocta- hedron or icosahedron, and 31p and t~ n.m.r, studies reveal a high mobility of ligands and/or Rh atoms. CO can be adsorb- ed irreversibly and forms terminal bonds with the surface Rh atoms.

* This terminology is misleading. As will be evident from Figure 1, the ligand is really a hydrazide(2-) containing a substituent with a thiolate, which carries the third unit of charge.

120 TMC literature highlights- 3 Transition Met. Chem. 10, 118-120 (1985)

The complexes [Pt4(~t2-CO)sL4] ( L = PEt3, PMe2Ph, PMePh2 Or PEt2Bu-t) have been prepared (231 and the structure of a monoclinic form of the species with L = PMezPh determined crystallographically. The Pt4(CO)sP4 core has approxi- mate Czv symmetry, the Pt4 unit being a highly distorted edge- opened tetrahedron with five edge-bridging CO and four terminal L groups. 31p and l~ n.m.r, spectral studies reveal equivalent phosphorus ligands and Pt atoms, and this was interpreted in terms of a time-averaging of all possible isom- eric edge-opened tetrahedra.

When Cu powder and [NEt4]I are heated in Me,CO, [NEt4]r and monoclinic and hexagonal forms of [NEt4][CuIa] are produced (z4). The x-ray crystallographic study of the hexagonal form of the latter species reveal that it Should be formulated as [NEt4]6[Cu6Ill]I, containing [Cu6Ilt] 5- in which the metal atoms form a trigonal prismatic arrangement. Two I atoms are tridentate and three tetradentate, and each Cu atom has overall tetrahedral geometry.

Treatment of [Au{P(C6Hll)2Ph)NO3] with NaBH4 in EtOH affords (as) [Aul6C13{P(C6Hll)2Ph}6]NO3. X-ray studies of this species showed that the cation has toroidal geometry based on a hexagonal ring of edge- and face-sharing tetrahedra having a common vertex. Reaction of anhydrous FeCIz with Ss, KSPh and [NEt4]CI �9 HzO in MeCN gives (26) [NEt4]3[Fe6S6C16]. The anion has a hexagonal prismatic geometry with alternating Fe and S atoms at the apices. The six C1 atoms are coordinated, one to each Fe atom, and the FeS3C1 subunit has tetrahedral geometry.

Addition of ethanolic polysulphide to a solution of Cu(OAc)2 �9 H20 , followed by [Ph4P]C1 in MeCN, gives (27) [PPh412[Cu4(S4)(Ss)2]0.4[Cu4(Ss)3]0. 6. The copper atoms in each anion form a tetrahedron and the six terminal atoms of the three polysulphide groups represent a bridge for each of the six edges of the metal tetrahedron. With a change in concen- tration of polysulphide and/or solvent, [PPh412[Cug(S4)(Ss)2]x- [Cu4($4)2(S5)]1-~ (x = 0.5; 0.8; 0.9) is formed. Reaction of HAuC14 with ethanolic polysulphide and [oPPh4] + gives [PPh4]2[AuzS8] (Figure 4; Au-Au distance 3.12 A).

S \ S _ A u _ S / s Figure 4. Structure of the anion in [au2S8] 2-,

Treatment of CuC12 �9 2H20 with NaSR (R = Me or CH2Ph) and elemental sulphur (18), or of Cu(acac)2 with polysulphide ion in EtOH-DMF (z9), gives [Cu6($4)3($5)] e- , isolated as the [PPh4] + salt. From crystallographic studies it was shown that two distorted copper tetrahedra share a common edge and two of the S~- groups defined five-membered CuSn rings. The third S~- group is not chelating, and the five sulphur atoms of the tetradentate $52- ligand form a total of six sulphur-copper bonds.

Crystallographic studies of [NEt4]2[Cu(SPh)3], obtained (3~) by reaction of [{Cu(PPh3)C1)4] with [NEh][SPh] in MeCN, show trigonal coordination of the Cu atom. Treatment of Cu 2+ with t-BuSH, NEt3 and [NEt4]Br in Me2CO-EtOH gives (3t) [NEt4][Cus(SBu-t)6]. In this cluster two Cu atoms are three- coordinate, and three are two-coordinate. All the thiolate ligands form doubly-bridged edges of a trigonal prism, whereas the five Cu atoms constitute a trigonal bipyramid. There is weak Cu-Cu interaction within the cage.

Reaction of Ag{S(C6H4CI-p)} with PPh3 in PhMe gives (32) [Ags(SAr)6(PPh3)5(C6HsMe)2 ]. The Ags(SAr)6 cage contains a basal unit of an irregular hexagon of alternating Ag and S atoms centred by an Ag atom with trigonal planar Ag(SAr)3 coordination. A trigonal planar podal unit, Ag(SAr)3, is paral- lel to the base plane and is attached to it by three S(podal)- Ag(basal) bonds. Tetrahedral coordination of each of the basal Ag atoms is completed by terminal PPh3 ligands and an Ag(PPh3)2 unit is attached to the podal Ag(SAr)3 group by two bridging SAr groups.

References

0) j. W. Failer, K. H. Chao and H. H. Murray, Organometallics, 3, 1231 (1984). - (2) M. E. E. Meijer-Veldman, J. L. de Boer, H. J. de Liefde-Meijer, A. M. M. Schreurs, J. Kroon and A. L. Spek, J. Orga- nometal. Chem., 269, 255 (1984). - (3) A. J. Bandy, F. G. N. Cloke, M. L. H. Green, D. O'Hare and K. Prout, Y. Chem. Soc., Chem. Comm., 240 (1984). - (4)M. L. H. Green, D. O'Hare and J. M. Wallis, J. Chem. Soc., Chem. Comm., 233 (1984). - (5) R. B. Crack- nell, A. G. Orpen and J. L. Spencer, J. Chem. Soc., Chem. Comm., 326 (1984. - (6) K. Isobe, A Vazquez de Miguel, A. Nutton and P. M. Maitlis, J. Chem. Soc., Dalton Trans., 929 (1984). - (7) S. G. Davies, J. Hibberd, S. J. Simpson, S. E. Thomas and O. Watts, J. Chem. Soc., Dalton Trans., 701 (1984). - (a) j. T. Gauntlett, B. F. Taylor and M. J. Winter, J. Chem. Soc., Dalton Trans., 420 (1984). - (9) H. P. Kim, S. Kim, R. A. Jacobson and R. J. Angelici, Organometallics, 3, 1124 (1984). - (~0)T. D. TiUey, R. A. Andersen and A. Zalkin, Inorg. Chem., 23, 2271 (1984).

(11) W. J. Evans, L. A. Hughes and T. P. Hanusa, J. Am. Chem. Soc., 106, 4270 (1984). - (12) H. Gampp, M. M. Roberts and S. J. Lippard, Inorg. Chem., 23, 2793 (1984). - (~3)R. Mattes and H. Scholand, Angew. Chem., 96, 375 (1984). - (~4) M. H. Chisholm, J. C. Huffmann and R. J. Tatz, J. Am. Chem. Soc., 106, 5385 (1984). - (15) L. B. Anderson, F. A. Cotton, D. Demarco, L, R. Falvetlo, S. M. Tetrick and R. A. Walton, J. Am. Chem. Soc., 106, 4743 (1984). - (16) W. A. Herrmann and J. L. Hubbard, J. Organometal. Chem., 262, C46 (1984). - (r~ K. K. Pandey, H. W. Roesky, M. Noltemeyer and G. IVl. Sheldrick, Z. Naturforsch., 39B, 590 (1984). - (~s) B. F. G. Johnson, J. Lewis and J. M. Mace, J. Chem. Soc., Chem. Comm., 186 (1984). - (19) B. F. G. Johnson, J. Lewis, W. J. H. Nelson, J. Puga, D. Braga, K. Henriek and M. McPartlin, J. Organometal. Chem., 266, 173 (1984). - (20) I. Bernal, H. Brunner, W. Meier, H. Pfisterer, J. Wach- ter and M. L. Zeigler, Angew. Chem., 96, 428 (1984).

(21) F. A. Cotton, D. O. Marler and W. Schwotzer, Inorg. Chim. Acta, 85, L31 (1984). - (a2)G. Schmid, U. Giebel, W. Huster and A. Schwenk, Inorg. Chim. Acts, 85, 97 (1984). - (23)A. Moor, P. S. Pregosin, L. M. Venanzi and A. J. Welch, Inorg. Chim. Acta, 85, 103 (1984).- (24)F. Mahdjour-Hassan-Abadi, H. Hartl and J. Fuchs, Angew. Chem., 96, 497 (1984). - (as) C. E. Briant, K. P. Hall, A. C. Wheeler and D. M. P. Mingos, ,1. Chem. Soc., Chem. Comm., 248 (1984). - (26) M. G. Kanatzidis, W. R. Dunham, W. R. Hagen and D. Coucouvanis, J. Chem. Soc., Chem. Comm., 256 (1984). - (27)A. Mueller, M. Roemer, H. Boegge, E. Krickemeyer and K. Schmitz, Inorg, Chim, Acta, 85, L39 (1984). - (~s) G, Henkel, P. Betz and B. Krebs, J. Chem. Soc., Chem. Comm., 314 (1984). - (49) A. M~ller, M. Roemer, H. Boegge, E. Krickemeyer and D. Bergmann, J. Chem. Soc., Chem. Comm., 348 (1984). - ~3o) D. C. Garner, J. R. Nicholson and W. Clegg, Inorg. Chem., 23, 2148 (1984).

(3~) G. A. Bowmaker, G. R. Clark, J. K. Seadon and I. G. Dance, Polyhedron, 3, 535 (1984). - (32) I. G. Dance, L. J. Fitzpatrick aM M. L. Scudder, Inorg. Chem., 23, 2276 (1984).

J. A. McCleverty

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