Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes
作者:Michael J. Sgro、Douglas W. Stephan
DOI:10.1039/c001312a
日期:——
DippDADNi(MeCO2CCCO2Me) (10), DippDABNi(Me3SiCCSiMe3) (11), DippDABNi(MeCO2CCCO2Me) (12) and DippBIANNi(MeCO2CCCO2Me) (13) were prepared. Reactions with olefins afforded DippDABNi(MeCO2CHCHCO2Me) (14), DippDABNi(MeCO2CHCHPh) (15). Employing isolated (3) or (15) in exchange reactions afforded (7), (11) (14) and (15). Similarly (6) served as a precursor to (10) while (11) reacts with PhCCPh to give (7). The solid
Well‐Defined Models for the Elusive Dinuclear Intermediates of the Pauson–Khand Reaction
作者:Douglas R. Hartline、Matthias Zeller、Christopher Uyeda
DOI:10.1002/anie.201601784
日期:2016.5.10
The mechanism of the Pauson–Khandreaction has attracted significant interest due to the unusual dinuclear nature of the Co2(CO)x active site. Experimental and computational data have indicated that the intermediates following the initial Co2(CO)6(alkyne) complex are thermodynamically unstable and do not build up in appreciable concentrations during the course of the reaction. As a consequence, the