2. G. A. Gailyunas, G. V. Nurtdinova, V. P. Yur'ev, G. A. Tolstikov, and S. R. Rafikov, Izv. Akad. Nauk SSSR, Ser. Khim., 914 (1982).

3. T. T. Vasil'eva, L. F. Germanova, V. I. Dostovalova, B. V. Nelyubin, and E. Kh. Freid- line, Izv. Akad. Nauk SSSR, Ser. Khim., 872 (1983).

4. R. Kh. Freidlina, T. T. Vasil'eva, G. A. Trapeznikova, and B. V. Nelyubin, Dokl. Akad. Nauk SSSR, 247, 1429 (1979).

5. T. T. Vasil'eva, L. F. Germanova, V. I. Dostovalova, B. V. Nelyubin, and R. Kh. Freid- lina, Izv. Akad. Nauk SSSR, Ser. Khim., 896 (1985).

6. A. B. Belyavskii and V. N. Kost, Izv. Akad. Nauk SSSR, Ser. Khim., 1514 (1963). 7. T. T. Vasil'eva, G. A. Trapeznikova, and B. V. Nelyubin, Izv. Akad. Nauk SSSR, Ser.

Khim., 635 (1979). 8. F. R. Mayo, J. Am. Chem. Soc., 70, 3689 (1948).

SYNTHESIS OF CATIONIC ALLYL CARBONYL COMPLEXES

OF GROUP VI METALS AND IRON

V. V. Krivykh, O. V. Gusev, P. V. Petrovskii, and M. I. Rybinskaya

UDC 542.91:541.49:547.361:546.725

The concurrent action of a strong protic acid and allyl alcohol or a conjugated diene on arene and cyclopentadienyl complexes of a series of transition metals upon UV irradia- tion gives allyl cationic complexes [1-5].

In the present work, we synthesized cationic allyl carbony! complexes not containing stabilizing hydrocarbon ligands since such complexes should be highly electrophilic. The synthesis of these compounds also held interest for determining the applicability of the synthetic factors and clarification of the factors affecting the formation of cationic allyl complexes.

Available group VI metal and iron carbonyls were used as the starting compounds. How- ever, the UV irradiation of these carbonyls and allyl alcohol or diene in the presence of 48% aqueous HBF 4 was not successful, which may be related to the insufficient acidity of the medium. Indeed, the use of anhydrous HBF4"Et20 gave complexes (I)-(III).

M(CO)n + CH 2 ---- CHCH2OFI + H B F a.Et~O [M(CO),,-~(~-CH~---CH :--=CH2)] + B F , -

( i ) - - ( r l I ) M = Fe, n = 5 (I); M = Mo, n ---- 6 ( I I ) ; M ---- W , n = 6 ( I I I ) .

The result of the reaction depends not only on the acidity of the medium but also on the nature of the metal. Thus, the allyl carbonyl complexes of Fe (I) [6] and W (III) are formed upon carrying out the reaction in ether, while the corresponding molybdenum deri- vative (II) is formed only upon using a solvent less basic than ether, viz., benzene. An allyl complex could not be obtained from Cr(CO)~ even under these conditions. This differ- ence in the behavior of group VI metal hexacarbonyls is apparently a consequence of the increase in basicity of the monotypic metal derivatives in the series Cr < Mo < W [7, 8].

While the Fe complex (I) and W complex (IIi) are rather stable compounds, their molyb- denum analog decomposes rapidly in solution and thus was characterized only by IR spectros- copy and elementa! analysis. The substitution of one CO group in Mo(CO)~ by P(OMe)3, which is a stronger donor, permits us to obtain stable complex (IV) in ether.

hw [(MeO)sPIMo(CO)5 + CH2=CHCH2OH + H B F ~ . E ~ 2 0 - - + {[(MeO)3P]Mo(CO)40]-CH2""CH'" "CH~)}+BF4 -

EtzO (IV)

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1400- 1404, June, 1986. Original article submitted January 31, 1985.

0568-5230/86/3506-1273 $12.50 �9 1986 Plenum Publishing Corporation 1273

In the case of Cr(C0)6, only the substitution of two carbonyl ligands by P(0Me) 3 leads to the formation of an unstable cationic complex, whose existence was indicated only by IR spectroscopy.

While the difference in behavior of allyl alcohol and dienes in the synthesis of catio- nic allyl complexes from arene and cyclopentadienyl carbonyl complexes is not significant [i, 5], it is apparent in the case of simple metal carbonyls. Thus, the UV irradiation of ethereal Fe(CO) 5 in the presence of HBF4-Et20 and butadiene leads to uncharged butadiene iron tricarbonyl complex (VI) [9] and not the cationic allyl complex (VII) as found when using allyl alcohol.

Fe(CO)5 + C4H6 ~- HBFa. Et20 ----+ [(CO)aFe (q2-C4He)] -~ (CO)3Fe (~4-C,H~) Et20 I

• (V) (VI) [(CO),Fe (~3-CHaCH " CH " CH2)]+BF4 -

(VII)

A p p a r e n t l y , (V) , which i s f o rm ed in t h e f i r s t s t e p , i s much more r a p i d l y c o n v e r t e d upon UV irradiation to (VI) in an intramolecular reaction than attacked by a proton to form (VII). Pettit [i0] and Gibson [ii] have reported that N4-diene iron carbonyl complexes are capable of undergoing conversion to N3-allyl cationic complexes, but in the case of a much more acid medium than in our case. Complex (VII) precipitates from the reaction mixture in the absence of UV irradiation using Fe2(CO)9, i.e., under conditions for the formation of ~2_ tetracarbonyl iron complexes [9], but the yield is low (18%). IR spectroscopy indicates that the solution contains a significant amount of (V), which cannot be completely protonated under the given conditions.

Fe2(eo)a -~ C, H6 ~- HBF, .E t20 ~ (V) + (VII)

In t h i s c a s e , an i n c r e a s e in t h e a c i d i t y o f t h e medium may be a c h i e v e d by r e p l a c i n g e t h e r by l e s s b a s i c b e n z e n e [ 1 2 ] , b u t b u t a d i e n e p o l y m e r i z e s u n d e r t h e s e c o n d i t i o n s . We h a v e found t h a t e v a p o r a t i o n o f t h e r e a c t i o n m i x t u r e t o d r y n e s s (and i n c r e a s i n g t h e a c i d c o n c e n t r a t i o n ) l e a d s t o an i n c r e a s e in t h e y i e l d o f ( V I I ) t o 78%, w h i l e complex ( I ) was o b t a i n e d in h i g h y i e l d when u s i n g a l l y l a l c o h o l in t h i s r e a c t i o n w i t h o u t c o n c e n t r a t i o n o f t h e s o l u t i o n .

I n t h e c a s e o f W(CO) 6, ~ 2 - b u t a d i e n e complex ( V I I I ) [13] i s a l s o fo rmed in t h e f i r s t s t e p and c a t i o n i c c r o t y l complex ( IX) i s n o t fo rmed a t a l l due t o t h e l o w e r b a s i c i t y o f ( V I I I ) in c o m p a r i s o n w i t h t h e Fe a n a l o g (V) ; ( IX) was o n l y o b t a i n e d by e v a p o r a t i o n o f t h e r e a c t i o n m i x t u r e .

hv (CO)sW (n2-C~H, W(CO)~ + C,H6 + HBF4.Et20 ~ ~ (VIII)

[(CO)sW (~s-CHaCH "" CH "" CH2)]+BFa - (IX)

A decrease in the formation of cationic allyl complexes also results from the presence of electron-withdrawing substituents in the diene molecule. For example, only (X) is formed in the reaction of Fe2(CO) 9 with 1,4-diphenyl-l,3-butadiene and HBF4"Et20 in ether. Upon evaporation of the reaction mixture, (X) gives cationic (XI) in 2% yield. The major product in this case is N4-diene complex (XII) [14].

Fe2(CO)9 -~ (PhCH=CH)2 -~ HBFa. Et20 > (CO)4Fe [N2-(PhCH=CH)~] ~t~o ]_ (x)

[(COhFe (n3-PhCH '''CH CHCH2Ph)]+BF4--~ (CO)3Fe [~-(PhCH=CH)21' (Xl) (xn)

Carrying out this reaction in benzene led to an increase in the yield of (XI) to 28%. The corresponding tungsten complex is not formed under these conditions.

These results indicate that ~2-diene complexes are intermediates in the formation of the cationic allyl carbonyl complexes, which was confirmed in some cases by IR spectros- copy. Apparently, n2-complexes are also formed in the case of allyl alcohol. An in- crease in the basicity of the intermediate n2-complexes in the series LCr(CO) S < LMo(CO)~ < LW(C0) s < LFe(C0)~, substitution of a carbonyl ligand by P(0Me) 3, which is a stronger donor, and an increase in the donor capacity of the organic substrate (Ch2=CH=0H > CH 2 = CHCH= CH 2 > PhCH= CHCH=CHPh) facilitate the formation of cationic allyl complexes,

1274

The compositions and structures of the complexes obtained were established by elemental analysis and IR and PMR spectroscopy. The spectral data for the Fe complexes (I) and (VII) correspond with the literature values [6]. On the whole, the PMR spectral pattern for the allyl ligand is analogous to that for previously obtained complexes [1-4]. Syn-methylallyl complexes are formed exclusively upon the use of butadiene, while syn,syn-l-phenyl-3-benzyl- allyl complex (IX) is formed in the case of diphenylbutadiene. Complex (IV) is a 3.5:1.0 mixture of cis and trans arrangement of the phosphite and allyl ligands in the octahedron. The predominant formation of the cis isomer was indicated by IR spectroscopy.

EXPERIMENTAL

All the operations in the syntheses of these compounds were carried out in an argon atmosphere using absolute solvents. Anhydrous HBF4"Et20 was obtained by mixing equivalent amounts of liquid HF and BF3"Et20.

The IR spectra were obtained in MeNO 2 solution on an IKS-29 spectrometer. The PMR spec- tra were taken in CF3CO2H solution on a Bruker WP-200SY spectrometer at 200, 13 MHz and a Tesla BS-467 spectrometer at 60 MHz. The chemical shifts are given on the 6 scale, ppm, re- lative to TMS.

Photochemical Preparation of Complexes (I)-(IV). A solution of 1 mmole carbonyl, 1.5 mmoles allyl alcohol, and 1.5 mmoles HBF4.Et20 in 70 ml solvent was irradiated for 7 h in a three-necked flask equipped with an internal cooling device. The precipitate that formed was washed with ether and dried.

Complex (I) was obtained in 88% yield (0.26 g). IR spectrum: 2160, 2092 cm -I. PMR spectrum: 3.26 d (2H, Hanti, J = 12.0 Hz), 4.24 d (2H, Hsy n, J = 7.0 Hz), 5.5-6.5 m (H, Hcent r) [6]. IR spectrum in CHINO2: 2160, 2100cm ":, PMRspectruminCH3CO2D: 2.35d.d (2H, Hanti, J1 = 12.0, J2 = 1.5 Hz), 4.24 d.d (2H, Hsyn, J1 = 6.0, J2 = 2.0 Hz), 5.8(5 m (H,

Hcentr).

Complex (II) was obtained in 48% yield (0.18 g). Found: C 25.91; H I~66%. Calculated for CBHsBF4MoOs: C 26.41; H 1.38%. IR spectrum: 2140, 2054, 2018, 1936 cm -I.

Complex (III) was obtained in 37% yield (0.16 g). Found: C 21.39; H 1.20%. Calculated for CBH~BF4OsW: C 21.72; H 1.12%. IR spectrum: 2144, 2054, 2018, 1936 cm -!. PMR spectrum in C6HsNO2:4.45 d (2H, Hanti, J = 12.1Hz), 5.34 (2H, Hsyn, J = 7.0 Hz), 6.31 m (H, Hcentr).

Complex (IV) was obtained in 54% yield (0.26 g). IR spectrum: 2110, 2055, 1994 cm -l PME spectrum for cis-(IV): 3.31 d (2H, Hanti, J = 11.8 Hz), 4.07 d (gH, P(OCH3)3, J = 11.8 Hz), 4.23 d.d (2H, Hsyn, J~ = 6.8, J2 = 1.7 Hz), 5.67 t.t (H, Hcentr), J~ = 11.8 J2 = 6.5 Hz). Trans-(IV): 3.52 d (2H, Hanti, J = 12.5 Hz), 4.10 d [gH, P(OCH3)~, J = 16.5 Hz], 4.47 d.d (2H, Hsyn, J1 =J2 =5.5Hz), 5.5-5.~m (H, Hcentr). The cis-(IV)/trans-(IV) ratio was 3.5:1.0.

Preparation of Complex (IX) L A solution of 0.35 g (i mmole) W(CO)6, 0.5 ml butadiene, and 0.2 ml (1.5 mmoles) HBF4"Et20 was irradiated for 7 h. The mixture obtained was evapora- ted to dryness. The residue was washed with ether, dissolved in nitromethane, and precip- itated with ether. The precipitate was filtered off, washed with ether, and dried to give 0.12 g (25%) (IX). IR spectrum: 2140, 2058, 2018, 1939 cm -I. PMR spectrum: 2.50 d (3H, CH3, J = 6.5 Hz), 3.59 d (H, Hanti , J = 12.0 Hz), 4.69 d (H, Hsyn, J = 6.5 Hz), 4.85 d.q (H, Hanti, Jl = 12.0, J2 = 6.5 Hz), 5.50 d.d.d (H, Hcentr, Jl = J2 = 12.0, J3 = 6.5 Hz).

Preparation of Complexes (I), (VII), and (XI) from Fe2(CO) 9___~. A sample of 1.5 mmoles allyl alcohol or dieneand 0.2mi (1.5 mmoles) HBF4.Et20 were added to a suspension of 0.36 g (i mmole) Fe2(C0) 9 in 50 ml solvent and stirred until the Fe2(CO) 9 was completely dissolved over 4-6 h. The precipitate that formed was filtered off, washed with ether, and reprecip- itated from nitromethane.

The yield of complex (I) was 90% (0.27 g). IR spectrum: 2160, 2092 cm -I.

The yield of complex (VII) was 13% (0.04 g) (evaporation of the reaction mixture gives an additional 0.20 g). IR spectrum: 2155, 2090 cm -I. PMR spectrum: 2.16 d (3H, CH3, J = 6.0 Hz), 3.00 d (H, Hanti , J = 12.0 Hz), 4.04 d (H, Hsyn, J = 6.5 Hz), 4.44 d.q (H, Hanti, J1 = 12.0, J2 + 6.0 Hz), 5.41 m (H, Hcent r) [6]. IR spectrum in CH3NO2: 2155, 2100, 2095, 2085 cm -I PMR spectrum (CF3CO2D): 2.15 d (3H, CH3, J = 7.0 Hz), 2.95 d.d (H, Hanti , J1 = 12.0, J2 = 3.0 Hz), 4.04 d.d. (H, Hsyn, J1 = 7.0, J2 = 3.0 Hz), 4.60 m (H, Hanti 0) , 5.65 m (H, Hcentr).

1275

Complex (IX) was obtained in 28% yield (0.13 g). IR spectrum: 2147, 2105, 2085 cm -I. PMR spectrum: 3.74, 3.85 (2H, CH2Ph, JAB = 16.1, Jl = 3.2, J2 = 4.4 Hz), 4.648 d.d.d (H, Hanti , Jz = 11.8, J2 = 4.4, J~ = 3.2 Hz), 5.140 d (H, Hanti, J = 11.8 Hz), 6.409 d.d (H, Hcentr, J1 = J2 = 11.8 Hz), 7.35-7.66 m (10H, 2C6Hs).

CONCLUSIONS

i. A method was developed for the direct~ one-step synthesis of allyl carbonyl com- plexes of iron, molybdenum, and tungsten, and the limits of the applicability of this method were determined.

2. The tendency to form cationic allyl complexes increases with increasing acidity of the medium and basicity of the complex and of the organic substrate.

LITERATURE CITED

I. A. N. Nesmeyanov, V. V. Krivykh, E. S. Taits, M. I. Rybinskaya, and G. K.-I. Magomedov, USSR Inventor's Certificate No. 794017 (1980); Byull. Izobret., No. i, 96 (1981).

2. A. N. Nesmeyanov, V. V. Krivykh, M. I. Rybinskaya, and E. S. Ii'minskaya, J. Organomet. Chem., 209, 309 (1984).

3. V. V. Krivykh, O. V. Gusev, and M. I. Rybinskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 644 (1983).

4. V. V. Krivykh, O. V. Gusev, P. V. Petrovskii, and M. I. Rybinskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 2635 (1983).

5. V. V. Krivykh, O. V. Gusev, and M. I. Rybinskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 1178 (1984).

6. J. Dieter and K. M. Nicholas, J. Organomet. Chem., 212, 107 (1981). 7. A. Davison, W. McFarlane, L. Pratt, and G. Wilkinson, J. Chem. Soc., 3653 (1962). 8. B. V. Lokshin, E. B. Rusach, V. S. Kaganovich, V. V. Krivykh, A. N. Artemov, and N. I.

Sirotkin, Zh. Strukt. Khim., 16, 592 (1975). 9. S. P. Gubin, in: Methods in Organic Chemistry [in Russian], Nauka, Moscow (1976), p. 7.

i0. G. F. Emerson and R. Pettit, J. Am. Chem. Soc., 84, 4591 (1962). ii. D. H. Gibson and R. L. Vonnahme, J. Am. Chem. Soc., 94, 5090 (1972). 12. R. Bell, The Proton in Chemistry, Chapman and Hall (1973). 13. I. W. Stolz, G. R. Dobson, and R. K. Sheline, Inorg. Chem., 2, 1264 (1963). 14. T. A. Manuel, S. L. Stafford, and F. G. A. Stone, J. Am. Chem. Soc., 83, 3597 (1961).

RING EXPANSION OF I-(CHLOROMETHYL)SILATRANE

V. M. Kilesso,* V. I. Kopkov, A. S. Shashkov, and B. N. Stepanenko*

UDC 542.91:547.1'128:547.455

We have previously reported [i] the reaction of sucrates of protected monoses and the alkoxides of monohydric alcohols with l-(chloromethyl)silatrane. As in the ring expansion of chloromethylated cyclic silicocarbohydrates by treatment with AICI~ [2, 3], this results in the expansion of one of the atrane rings to givehomosilatranes (Table I):

~H2OCH2CH~- I

RONa ~ C1CH2ii(OCH~CH~)~ " ~ . ROSi(OCH2CH2)2i -~- NaC1

where R = Me (I), Et (II), CH2CH2CHCH2CH20 (III), and C~H!I (IV), together with the mono- saccharide residues 1,2;5,6=di-O-isopropylidene-a-D-glucofuranose (V), 1,2;3,4-di-O-iso- propylidene-a-D-galactopyranose (VI), 2,3;4,5-di-O-isopropylidene-8-D-fructopyranose (VII),

* Deceased.

N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1404-1408, June, 1986. Original article submitted January 15, 1985.

1276 0568-5230/86/3506-1276 $12.50 �9 1986 Plenum Publishing Corporation