Computational Discovery of Stable Transition-Metal Vinylidene Complexes

Autor:	Adrian C. Whitwood, Benjamin W. Rawe, Elizabeth J. Smith, Iman G. Khazal, Jason M. Lynam, Natalie Fey, Keshan Bolaky, Oliver J. S. Pickup, Timothy C. King
Rok vydání:	2014
Předmět:	chemistry.chemical_classification Chemistry Organic Chemistry Alkyne Combinatorial chemistry Oxidative addition Tautomer Coupling reaction Inorganic Chemistry Transition metal Electronic effect Moiety Organic chemistry Physical and Theoretical Chemistry Group 2 organometallic chemistry
Zdroj:	Organometallics. 33:1751-1761
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om500114u
Popis:	Experimental results have long suggested that catalyst optimization is an inherently multivariate process, requiring the screening of reaction conditions (temperature, pressure, solvents, precursors, etc.), catalyst structure (metal and ligands), and substrate scope. With a view to demonstrating the feasibility and utility of multivariate computational screening of organometallic catalysts, we have investigated the structural and electronic properties of a library of transition-metal-coordinated alkyne and vinylidene tautomers in different coordination environments. By varying the substituents on the organic moiety of 60 alkyne/vinylidene pairs we were able to capture and quantify the key structural and electronic effects on tautomer preference. For a carefully selected subset of substituents, the effects of metal and ancillary ligands were then explored. We have been able to formulate a protocol for assessing the stabilization of vinylidenes in transition-metal complexes, suggesting that the d6 square-ba...
Databáze:	OpenAIRE
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