Intermediates in the decomposition of aliphatic diazo-compounds. Part VIII. The mechanism of ether formation from diarylmethylenes and alcohols
作者:D. Bethell、A. R. Newall、D. Whittaker
DOI:10.1039/j29710000023
日期:——
The thermal decomposition of diphenyldiazomethane and its 4,4′-dichloro-, 4,4′-dimethoxy-, and 4,4′-dimethyl analogues at 85 °C in acetonitrile containing methyl and t-butyl alcohols (ca. 1M) has been studied. Kinetic studies indicate that the major reaction product, the alkyl diarylmethyl ether, is formed by attack of intermediate diarylmethylene on the alcohol. The relative reactivities of methyl and
Enhanced Electrophilicity of Heterobimetallic Bi–Rh Paddlewheel Carbene Complexes: A Combined Experimental, Spectroscopic, and Computational Study
作者:Lee R. Collins、Maurice van Gastel、Frank Neese、Alois Fürstner
DOI:10.1021/jacs.8b08384
日期:2018.10.10
accounting for the observed enhancement in bismuth-rhodium carbene electrophilicity. These findings are supported by a detailed spectroscopic study of the "donor-donor" carbenecomplexes Rh2(esp)2C( p-MeOPh)2 (19) and BiRh(esp)2C( p-MeOPh)2 (20), employing a combination of UV-vis and resonance Raman spectroscopy. The results reveal that carbene chemoselectivity in MRh(L)4 catalysis can be modulated to