Direct observation of. alpha.-hydrogen transfer from alkyl to alkylidyne ligands in (Me3CCH2) 3W: CSiMe3. Kinetic and mechanistic studies of alkyl-alkylidyne …

KG Caulton, MH Chisholm, WE Streib…

文献索引：Caulton, Kenneth G.; Chisholm, Malcolm H.; Streib, William E.; Xue, Ziling Journal of the American Chemical Society, 1991 , vol. 113, # 16 p. 6082 - 6090

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被引用次数: 57

摘要

Abstract: a-Hydrogen atoms in (Me3CCHz), WeSiMe3 are found to migrate to the a-carbon atom of the alkylidyne ligand leading to the equilibrium (Me3CCH2), W= CSiMe3 (2a) s (Me, CCHz) z (Me3SiCHz) W= CCMe3 (2b). The equilibrium has been observed to follow reversible first-order kinetics with AH"= 2.3 (0.5) kcal mol-'and AS"= 8.1 (1.3) eu. The activation parameters for the conversion 2a-2b are AH*= 27.5 (0.6) kcal mol-'and AS'=-2.0 ...