Summary
Reactions of L = PHPh2 or PMePh2 with [MCl(CO)2(η3-C3H4R)(MeCN)2] (M = Mo, R = H or Me; M = W, R = H) in MeOH involve initial substitution to give [MCl(CO)2(η3-C3H4R)L2]. In MeCN, an excess of tertiary phosphine readily causes reductive elimination of allyl halide with the formation ofmer-[M(CO)2(MeCN)L3]. The molybdenum analogue can also be produced in high yields by reacting PMePh2 with either [Mo(CO)2(η3-C3H5)(MeCN)3]BF4 or Ph4As[Mo2Cl3(CO)4(η3-C3H5)2]. During these reactions, the new [MCl2(CO)2(η3-C3H5)(PMePh2)]− anions were formed and isolated as their σ-allylphosphonium salts. Under forcing conditions, reactions involving PHPh2 also resulted in elimination of the allyl group giving high yields ofcis-M(CO)2(PHPh2)4. The relevance of these observations on the mechanism of the reduction process are discussed.
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Brisdon, B.J., Edwards, D.A. & Paddick, K.E. Reactions of diphenylphosphine and methyldiphenylphosphine with (η3-allyl)dicarbonylchlorobis(methyl cyanide)molybdenum and-tungsten: Mechanistic implications in the reductive elimination of allyl halides. Transition Met Chem 6, 83–86 (1981). https://doi.org/10.1007/BF00626111
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DOI: https://doi.org/10.1007/BF00626111