Yunzhe Jiao, W. Brennessel, W. Jones
Apr 15, 2015
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Influential Citations
19
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Journal
Organometallics
Abstract
The reactive fragment [Tp′Rh(PMe3)], generated from the thermal precursor Tp′Rh(PMe3)(Me)H, is found to cleave the C–Cl bonds of chlorohydrocarbons under mild conditions. Reaction with chloromethane gives clean formation of an initial C–H activation product, which rearranges to form the C–Cl activation product at 30 °C. Reaction with dichloromethane or benzyl chloride gives a mixture of C–Cl activation products as well as products from chlorination. Reaction with chlorocyclohexane gives a mixture of intermediates from C–H activation, which react further upon heating to give a C–Cl cleavage product as well as the β-chloride elimination product Tp′Rh(PMe3)(Cl)H plus cyclohexene. Complete conversion from a C–H activation product to a C–Cl activation product was observed in the reaction with 1,2-dichloroethylene, where β-elimination is circumvented. Activation of 1-chlorobutane, 1,2-dichloroethane, or 1,4-dichlorobutane gives a mixture of C–Cl activation products as well as Tp′Rh(PMe3)(Cl)H plus olefin. Simil...