Chiral [Mo3S4H3(diphosphine)3]+ hydrido clusters and study of the effect of the metal atom on the kinetics of proton transfer to the coordinated hydride: Mo vs W
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http://dx.doi.org/ 10.1021/ic100381u |
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Título
Chiral [Mo3S4H3(diphosphine)3]+ hydrido clusters and study of the effect of the metal atom on the kinetics of proton transfer to the coordinated hydride: Mo vs WAutoría
Fecha de publicación
2010Editor
American Chemical SocietyISSN
0020-1669Cita bibliográfica
Inorganic Chemistry (2010), 49, 13, p. 5935–5942Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://pubs.acs.org/doi/full/10.1021/ic100381uVersión
info:eu-repo/semantics/publishedVersionResumen
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 ... [+]
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. [-]
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