Chiral [Mo3S4H3(diphosphine)3]+ hydrido clusters and study of the effect of the metal atom on the kinetics of the acid-assisted substitution of the coordinated hydride: Mo vs W.

The molybdenum(IV) cluster hydrides of formula [Mo(3)S(4)H(3)(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 [Mo(3)S(4)H(3)((R,R)-Me-BPE)(3)](+) as well as its tungsten analogue are obtained in optically pure forms. Reaction of the incomplete cuboidal [M(3)S(4)H(3)((R,R)-Me-BPE)(3)](+) (M = Mo, W) complex with acids in CH(2)Cl(2) solution shows kinetic features similar to those observed for the related incomplete cuboidal [W(3)S(4)H(3)(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 [M(3)S(4)H(3)((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.