Formation of the Alkoxyalkyl Complexes (CO)2(η-C5H4R)> (M = Mo, R = H; M = W, R = H or Me) and their Transformations by Loss of MeOH into η3-Propenoyl or Vinyl Complexes. Crystal Structures of (CO)2(PPh3)(η-C5H5>BF4, 3-CH2CHC=O)(CO)(PPh3)(η-C5...

DOI: 10.1039/DT9910001117

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1117 - 1128 (1991)

Update date:2022-08-31

Topics:

Authors:

Adams, Harry

Bailey, Neil A.

Gauntlett, J. Trevor

Harkin, Ian M.

Winter, Mark J.

Woodward, Simon

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Article abstract of DOI:10.1039/DT9910001117

Addition of MeSO3F or BF4 followed by PPh3 to the aldehyde complex (1-) results in formation of the methoxyalkyl complex trans-(CO)2(PPh3)(η-C5H5)> in a reaction that proceeds via the unstable 3-CHMe(OMe)>(CO)2(η-C5H5)>.A by-product of this reaction is the ylide trans-(CO)2(PPh3)(η-C5H5)>X (X = BF4(1-) or SO3F(1-)), a species (X = BF4) better prepared by treatment of trans-(CO)2(PPh3)(η-C5H5)> with HBF4 in the presence of PPh3.The crystalline ylide trans-(CO)2(PPh3)(η-C5H5)>BF4 is monoclinic, with a = 11.378(34), b = 18.903(35), c = 20.17(8) Angstroem, β = 115.28(31) deg and for the 3918 independent reflections with I/?(I) > 3.0, R = 0.0510.In solution, trans-(CO)2(PPh3)(η-C5H5)> either degrades to or loses MeOH to form the η³-propenoyl 3-CH2CHC=O)(CO)(PPh3)(η-C5H5)>.This molecule is monoclinic, with a = 17.231(50), b = 8.189(14), c = 16.727(36) Angstroem, β = 106.79(22) deg and for the 1654 independent reflections for which <*>F<*>/?(<*>F<*>) > 4.0, R = 0.100.The proposed mechanism for its formation is based on isotopic tracking experiments and includes a vinyl to carbonyl migration.Treatment of (R = H or Me) with PPh3 in MeCN gives the acyl .These react with to form the cationic carbenes (CO)2(PPh3)(η-C5H4R)>BF4, which in turn react with LiBHEt3 to give the alkoxyalkyls trans-(CO)2(PPh3)(η-C5H4R)>.The alkoxyalkyls trans-(CO)2(PPh3)(η-C5H4R)> react with traces of acid to form the ?-vinyls trans-, the methylcyclopentadienyl species of which is crystalline, monoclinic, with a = 36.952(40), b = 10.971(13), c = 25.148(23) Angstroem and β = 103.60(8) deg.For the 2542 independent reflections for which <*>F<*>/?(<*>F<*>) > 5.0, R converged to 0.0750.

Full text of DOI:10.1039/DT9910001117

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