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• W1991945868 abstract "Reactions at mild temperatures of the acetonitrile adducts [M(CO)3(NCMe)3] (M = Mo (1), W (2)) with various substituted cyclopentadienes in THF give the hydrido derivatives [MH{η5-C5R4Si(CH3)2-(CH2CHCH2)}(CO)3] (M = Mo, R = H (5a), R = CH3 (6), M = W, R = H (7a), R = CH3 (8a)) and [MoH{η5-C5R4R‘}(CO)3] (R = CH3, R‘ = H (16); R = H, R‘ = SiMe3 (17)) in isolated yields of 60−70%. THF solutions of derivatives 5a, 7a, and 8a undergo isomerization of the cyclopentadienyl-tethered-allyl unit to give the corresponding methyl-vinyl-dimethylsilyl-η5-cyclopentadienyl hydrido compounds [MH{η5-C5R4Si(CH3)2(CHCHCH3)}(CO)3] (M = Mo, R = H (5b), M = W, R = H (7b), R = CH3 (8b)) in final a:b ratios of ca. 2:1, 2:1, and 1:1, respectively. Solvent polarity seems to be crucial in these transformations. Dehydrogenation and desilylation of 5a in THF solutions to give the dinuclear derivative [Mo{η5-C5H4Si(CH3)2(CH2CHCH2)}(CO)3]2 (9) and [MoH(η5-C5H5)(CO)3] (15), respectively, are processes competitive with the allyl isomerization. Treatment of 5a and 7a with equimolar amounts of ONMe3 permits isolation of pure compound 9 and [W{η5-C5H4Si(CH3)2(CH2CHCH2)}(CO)3]2 (10) in isolated yields of 80−90%. Coordination of the olefin pendant unit to the metal was detectable only by reaction of 5a and 7a with [CPh3][B(C6F5)4] to give the cationic species [M{η5-C5H4Si-(CH3)2(CH2CHCH2)}(CO)3][B(C6F5)4] (M = Mo (18), W (19)). Molecular structure determinations by X-ray diffraction methods for derivatives 8a and 9 are also reported." @default.
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• W1991945868 date "2007-06-14" @default.
• W1991945868 modified "2023-09-27" @default.
• W1991945868 title "Allyl Isomerization Mediated by Cyclopentadienyl Group 6 Metal Compounds" @default.
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• W1991945868 doi "https://doi.org/10.1021/om700293a" @default.
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