Chiral [Mo3S4H3(diphosphine)3]+ Hydrido Clusters and Study of the Effect of the Metal Atom on the Kinetics of the Acid-Assisted Substitution of t

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• 作者：Andrs G. Algarra ; Manuel G. Basallote ; M. Jess Fernndez-Trujillo ; Marta Feliz ; Eva Guillamn ; Rosa Llusar ; Ivan Sorribes ; Cristian Vicent
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：July 5, 2010
• 年：2010
• 卷：49
• 期：13
• 页码：5935-5942
• 全文大小：890K
• 年卷期：v.49,no.13(July 5, 2010)
• ISSN：1520-510X

文摘

The molybdenum(IV) cluster hydrides of formula [Mo₃S₄H₃(diphosphine)₃]⁺ with diphosphine = 1,2-(bis)dimethylphosphinoethane (dmpe) or (+)-1,2-bis-(2R,5R)-2,5-(dimethylphospholan-1-yl)ethane ((R,R)-Me-BPE) have been isolated in moderate to high yields by reacting their halide precursors with borohydride. Complex [Mo₃S₄H₃((R,R)-Me-BPE)₃]⁺ as well as its tungsten analogue are obtained in optically pure forms. Reaction of the incomplete cuboidal [M₃S₄H₃((R,R)-Me-BPE)₃]⁺ (M = Mo, W) complex with acids in CH₂Cl₂ solution shows kinetic features similar to those observed for the related incomplete cuboidal [W₃S₄H₃(dmpe)₃]⁺ cluster. However, there is a decrease in the value of the rate constants that is explained as a result of the higher steric effect of the diphosphine. The rate constants for the reaction of both clusters [M₃S₄H₃((R,R)-Me-BPE)₃]⁺ (M = Mo, W) with HCl have similar values, thus indicating a negligible effect of the metal center on the kinetics of reaction of the hydrides coordinated to any of both transition metals.