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Comprehensive Computational Study of Decamethyldizincocene Formation. 1. Reaction of ZnR2 Reagents with Decamethylzincocene

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journal contribution
posted on 2016-02-19, 07:07 authored by Steven S. Hepperle, Yan Alexander Wang
Computational methods were used to study the surprising 2004 synthesis of decamethyldizincocene, Zn25-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.