Mechanism of Olefin Insertion into Metal-Oxygen Bonds. Reaction of [(C6H5)2PCH2CH2P(C6H5)2]Pt(CH3)(OCH3) with Tetrafluoroethylene

Organometallics

Volumn 4, Issue 2, 1985, Pages 406-408

  Bryndza, Henry E ^a  

^a DUPONT COMPANY   (United States)

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Indexed keywords

EID: 0001458913     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om00121a041     Document Type: Article

References (5)

1. A catalytic olefin hydration might involve (a) initial activation of an OH bond in water by a low-valent metal, (b) coordination of an olefin, followed by (c) olefin insertion into the M-O bond of the hydrido-hydroxo complex thus generated, and finally (d) the reductive elimination of product alcohol from a cis alkyl hydride to regenerate the low-valent metal catalyst. Step a is well precedented as is step d. (a) Yoshida, T.; Matsuda, T.; Okano, T.; Kitani, T.; Otsuka, S. J. Am. Chem. Soc. 1979, 101, 2027–2038. (b) Yoshida, T.; Ueda, Y.; Otsuka, S. J. Am. Chem. Soc. 1978,100, 3941–3942. (c) Arnold, D. P.; Bennett, M. A. J. Organomet. Chem. 1980,199,119-35. (d) Jones, R. F.; Cole-Hamilton, D. J. J. Chem. Soc., Chem. Commun. 1981, 58–9. (e) Halpem, J.; Abis, L.; Santi, R. J. Organomet. Chem. 1981,215, 263–7. (f) Halpem, J.; Sen, A.; Abis, L. J. Am. Chem. Soc. 1978, 100, 2915–6. (g) Balazs, A. C.; Johnson, K. H.; Whitesides, G. M. Report TR-14; order #AD-A096 408; 1981. (h) Hill, R. H.; Puddephatt, R. J. Inorg. Chim. Acta 1981, 54, L277-L278. (i) Sostero, S.; Traverso, O.; Ros, R.; Michelin, R. A. J. Organomet. Chem. 1983, 246, 325–9.
2. The insertion of olefins into metal-oxygen bonds as a mechanistic step of the Wacker oxidation is still the subject of some debate. We are unaware of any simple olefin which has been shown to insert into metal-oxygen bonds, though examples of nucleophilic attack of oxy nucleophiles on coordinated olefins are well-known. Relevant articles to this controversy follow: (a) Stille, J. K.; Morgan, R. A. J. Am. Chem. Soc. 1966,88,5136-5141. (b) Green, M.; Hancock, R. I. J. Chem. Soc. A 1967, 2054–2057. (c) Shaw, B. L. J. Chem. Soc., Chem. Commun. 1968, 464. (d) Stille, J. K.; Fox, D. B. Inorg. Nucl. Chem. Lett. 1969,5,157-161. (e) Green, M.; Sashan, J. K. K.; Al-Najjar, I. M. J. Chem. Soc., Dalton Trans. 1981,1565-71. (f) Clark, H. C.; Goel, A. B.; Goel, S. J. Organomet. Chem. 1981, 216, C25-C28. (g) Bäckvall, J. E.; Nordberg, R. E. J. Am. Chem. Soc. 1981,103, 4959–60. (h) Stille, J. K.; Devakaruni, R. J. Am. Chem. Soc. 1978,100,1303-4. (i) Zaw, K.; Lautens, M.; Henry, P. M. Organometallics 1983,2,197-9. (j) Wan, W. K.; Zaw, K.; Henry, P. M. J. Mol. Catal. 1982,16, 81–7. (k) Gragor, N.; Henry, P. M. J. Am. Chem. Soc. 1981,103, 681–2. (1) Henry, P. M. “Palladium-Catalyzed Oxidation of Hydrocarbons”; D. Reidel Publishing Co.: Dordrecht, Netherlands, 1980; Vol. 2.
3. H.E., Bryndza, J.C., Calabrese, S.S., Wreford, Organometallics, DPPE = bis(1,2-diphenylphosphino)ethane (C, 6, H, 6, ), 2, PCH, 2, CH, 2, P(C, 6, H, 5, ), 2, ]., (1984), 3, 1603-1604
4. 4 solution (which is 6 Hz shifted from the 0.04 M TFE solution). Precedent has been established for tetrafluoroethylene coordination to bis(phosphine)platinum(II) alkyl complexes prior to insertion of that olefin into platinum-carbon or platinum-hydrogen bonds. See: (a) Clark, H. C.; Puddephatt, R. J. Inorg. Chem. 1971,10,18-25. (b) Clark, H. C.; Puddephatt, R. J. Inorg. Chem. 1970, 9, 2670–2675.
5. Which is particularly interesting in light of calculations in: Bäckvall J. Am. Chem. Soc. 1984,106, 4369–4373 which suggest hydroxide ligands will always migrate more slowly to coordinated olefins (on four-coordinate Pd complexes) than alkyl ligands.