Journal of the American Chemical Society
2544
complex mixture; the products of the solid-state reaction could not be detected by the TLC analysis. (5) D. Lelbfrltz and J. D. Roberts, J. Am. Chem. SOC.,0 5 , 4996 (1973). (6) The 13C NMR spectrum of 4 was carried out in perdeuterated acetic acid, because of Its low solubility In methanol. However differences in chemical shifts between the two solvents are not exceeding 0.1-0.6 ppm, except for Co, C12,and HOC(CH3)2carbons (0.5-1.5 ppm). This could be demonstrated from comparative studies of 2 and 3 in both solvents. (7) The dehydration was carried out according to the procedure of E. Kelnan and Y. Mazur, private communication: 3 % FeC13 supported on Si02 was suspended with 0.5% 2 and 3 in methanol and dried under vacuum for 1, h; this was followed by extraction of the steroid with methanol and precipitation of the Feci3 with Na2HC03. (8) The Oxidation was perfotmed as described by Donald G. Lee In "Oxidation", Vol. 1, R. L. Augustine, Ed., Marcel Dekker, New York, N.Y., 1969, p 17. The high resolution mass spectrometric analysis is consistent with structure 6. The two most characteristic fragments obtained in addition to the mo-
c, 95
Hydride Donation Reactions of Transition Metal Formyl Complexes Sir: We recently developed a new synthesis of metal formyl complexes,I which have been proposed as important intermediates in the metal catalyzed reduction of C O by Hza2The availability of metal formyl complexes has allowed us to study their kinetic and thermodynamic stability and their chemical reactivity. Here we report that metal formyl complexes can act as hydride donors to electrophilessuch as ketones, alkyl halides, and metal carbonyls. Whereas Et4N+ trans- [(C6HsO)3P](CO)3FeCHO- (1) decomposes to Et4N+(C0)4FeH- and (C6HsO)# with a half-life of ~1 h at 67 "C in tetrahydrof~ran,~ attempts to obtain a IH N M R spectrum of 1 in acetone46 at ambient temperature led to disappearance of the formyl hydrogen resonance at 6 14.9 within 25 min and suggested that 1 had reacted with acetone. Reaction of 1 with 2-butanone overnight at ambient temperature followed by acid hydrolysis gave a 95% yield of 2-butano1, as determined by gas chr~matography.~ The
0002-7863/78/1500-2544$01 .OO/O
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0
lecular peaks are Band C. See Z. V. Zaretskil in "Mass Spectrometry of Steroids", Wliey, New York, N.Y., 1976, p 11. (10) The complex 1 (2C24H400&3HeO) crystallizes in space group P21212~; a = 25.809 (5), b = 13.610 (2), c = 7.233 (1) A; 2 = 4 molecules of 1 and 2 molecules of acetone: Dc = 1.102 g ~ m - The ~ . crystal structure was determined wlth an R factor of 0.10 for 2505 reflections. (11) P. E. M. Craven and 0. T. DeTitta, J. Chem. SOC.,Chem. Commun., 530 (1972). (12) S. C. De Sanctls, E. Giglio, V. Pavel, and C. Quagllata, Acta Crystallogr., Sect. 8, 26, 3656 (1972). (13) Because of the change In hybridization and bond length of the carbonyl group upon excitation, a slight difference of the geometrical picture as described by the x-ray analysis of the ground state 1s expected. For a discussion, see J. c. D. Brand and D. G. Wllllams, Adv. Phys. Org. Chem., 1, 365 (1963). (14) In the Intramolecular hydrogen abstractions described in ref 3, the allyllc abstractable hydrogens are In the plane of the keto group. (15) The crystal structure of C24H3804-CsHeO was measured in a closed caplllary saturated with acetone vapor. R crystallizes In a space group ~ 2 1 2 ~ 2 ~ ; a = 24.47, b = 14.26, c = 7.50 A; 2 = 4 molecules of 6 and 4 molecules of acetone; Dc = 1.129 g cm+. The crystal structure was determined wlth an R factor of 0.08 for 2579 reflections. (16) For a dlscusslon of the condltlons on hydrogen abstraction8 in rigid cyclic systems, see F. D. Lewis, R. W. Johnson, and R. A. Ruden, J. Am. Chem. Soc., 04, 4292 (1972).
Meir Lahav,* Les Leiserowitz,* Ronit Popovitz-Biro Chia-Pin Tang Department of Structural Chemistry The Weizmann Institute of Science, Rehouot, Israel Received September 28, 1977
100.8
possibility that 2-butanone is reduced by (C0)dFeH- formed in situ is excluded since 1 reacts with 2-butanone much faster than it decomposes to (C0)dFeH- and since no reaction between (C0)4FeH- and 2-butanone was observed by infrared spectroscopy. Reaction of a T H F solution of 1 (0.346 mmol) with CF3C02H (10 equiv) led to the formation of CH3OH (0.095 mmol, 27%) and no observable formaldehyde ( EtdN+ trans-[C6HsO3P] (CO)3FeCHO-. The possibility that these transformylations proceed via decarbonylation to give a metal hydride which then Binuclear and Mixed Metal Formyl Complexes: transfers hydride to a metal carbonyl is excluded since the Isolation, Characterization, and Chemistry reaction of 1 with Re2(CO)lo or Fe(C0)5 is faster than decomposition of l to (C0)dFeH- and since Et4N+(C0)4FeHSir: does not react with Re2(CO)lo, Fe(C0)5, or (C0)dFePCarbon monoxide-hydrogen gas mixtures can be trans(OC6H5)3 under the reaction conditions. formed by heterogeneous catalysts at high temperatures and [(C6H,0),P]( C0)3FeCHO- + h 2 ( C O ) l o pressures to methane, alcohols, and gasoline (Fischer-Tropsch 1 The initially formed intermediate in these reactions is believed to be the surface-bound formyl
It
( C ~ H S ~ ) ~ P F ~ (+C (CO)yRe2CHOO)~
--
+ Fe(CO),
It Re,(CO),o t (CO)4FeCHO-
Acknowledgment. Support from the Division of Basic Energy Sciences of the Department of Energy is gratefully acknowledged. We thank Professor John Gladysz (UCLA) for informing us of his similar results prior to publication. Supplementary Material Available: Preparation of 4 and 5 (2 pages). Ordering information is given on any current masthead page.
References and Notes (1)
C.P. Casey and S. M. Neumann, J. Am. Chem. SOC.,98,5395 (1976): see
also S. R. Winter, G. W. Cornen, and E. A. Thompson, J. Organornet. Chem., 133, 339 (1977). (2) 0. Henrici-Oilve and S.Olive, Angew. Chem., lnt. Ed. Engl., 15, 136 (1976). For other reviews of the Flscher-Tropsch reaction, see (a) M. A. Vannice, J. Catel., 37, 449, 462 (1975); (b) H. H. Storch, N. Golumblc, and R. 8. Anderson, "The Fischer-Tropsch and Related Synthesis", Wlley, New York, N.Y., 1951: (c) P. H. Emmett, Ed., "Catalysis", Voi. 4, Relnhold, New York, N.Y., 1956. (3) C. P. Casey and S. M. Neumann, unpublished results. (4) l/e in. X 20 ft 20% UCON 50 HB 280X on 60/80 Chrom P column at 85 OC. (5) The formation of formaldehyde on acldlficatlon of (CO),FeCHO- solutions has been prevlously reported by Collmane and confirmed by us.' (6) '/4 In. X 15 ft 10% Ethofat 60125 on 40160 Fiuoropak 80 column at 110
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methane, methanol, h i g h e r alkanes, a n d alcohols
1
The rational development of milder, homogeneous, and more selective Fischer-Tropsch-type processes5 requires the study of homogeneous homologues of 1 and other surface-bound intermediates on the reaction coordinate between C O and alkanes and alcohols. In this communication, we report (a) the synthesis of the first isolable binuclear formyl complex (2) by reaction of Li(C2H5)3BH with Re2(CO)lo, (b) the availability of the kinetically less stable mixed metal formyl complex 3 by reaction of Li(C2H5)3BH with ReMn(CO)lo, (c) reactions which establish 2 and 3 as potent hydride donors, and (d) the formation of formaldehyde and methanol from K+-2. 0
0
I1
Li+(CO),hRe(CO),(CH) 2
I1
Li+(CO),M'M(CO),(CH) 3 , M, M'= R e , hln 0
I1
Li+(C O ) . M n I k ( CO )& CH) 4
0 1978 American Chemical Society
