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Download fileComprehensive Computational Study of Decamethyldizincocene Formation. 1. Reaction of ZnR2 Reagents with Decamethylzincocene
journal contribution
posted on 2016-02-19, 07:07 authored by Steven
S. Hepperle, Yan Alexander WangComputational
methods were used to study the surprising 2004 synthesis
of decamethyldizincocene, Zn2(η5-C5Me5)2, which was the first molecule
to have a direct, unbridged bond between two first-row transition
metals. The computational results show that the methyl groups of decamethylzincocene,
Zn(η5-C5Me5)(η1-C5Me5), affect the transition-state stability
of its reaction with ZnEt2 (or ZnPh2) through
steric hindrance, and this could possibly allow a counter-reaction,
the homolytic dissociation of Zn(η5-C5Me5)(η1-C5Me5)
into Zn(η5-C5Me5)• and (η1-C5Me5)•, to occur, and because no such steric hindrance occurs when zincocene,
Zn(η5-C5H5)(η1-C5H5), is used as a reactant, its dissociation
never occurs regardless of what ZnR2 reagent is used.