Rotation of the η3‐Propargyl Ligand in [(C6Me5H)M(CO)23‐C3H3)]+ (M=Cr, Mo, W) Complexes

Author:

Chamkin Aleksandr A.1ORCID,Taits Elena S.1ORCID,Krivykh Vasily V.1ORCID

Affiliation:

1. A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences 119334 Moscow Vavilova St. 28, bld. 1, INEOS Russia

Abstract

AbstractThe dynamic behaviour of η3‐propargyl ligand in [(C6Me5H)M(CO)23‐C3H3)]+ (comp : M, M=Cr, Mo, W) complexes was systematically studied using computational chemistry approaches. Two isomerization pathways were assessed: a simple rotation of the propargyl fragment around the metal‐ligand axis and the η3‐η1 hapticity slippage of the propargyl ligand. The former mechanism possesses the activation energies of +25.9 (comp : Cr), +20.7 (comp : Mo), and +20.3 kcal mol−1 (comp : W) and is feasible at near‐room temperatures. The η3‐η1 partial decoordination requires essentially the same energy for comp : Cr (+25.8 kcal mol−1) but is hindered for comp : Mo and comp : W (>+30 kcal mol−1). To analyse the factors that influenced these trends, the binding of analogous comp : M and η3‐allyl complexes was studied using the local energy decomposition method.

Funder

Ministry of Science and Higher Education of the Russian Federation

Publisher

Wiley

Subject

General Chemistry

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