Resumen de Detection of Pd(III) and Pd(IV) Intermediates during the Aerobic Oxidative C–C Bond Formation from a Pd(II) Dimethyl Complex
Fengzhi Tang, Ying Zhang, Nigam P. Rath, Liviu M. Mirica
The dimethyl PdII complex (MeN4)PdIIMe2 (MeN4 = N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane) is readily oxidized by dioxygen in the presence of protic solvents to selectively eliminate ethane. UV–vis, EPR, ESI-MS, and NMR studies reveal the formation of several PdIII and PdIV intermediates during the aerobically induced C–C bond formation reaction, including the key intermediate [(κ3-MeN4)PdIVMe3]+, which leads to ethane elimination. The latter complex was also synthesized independently and structurally characterized to reveal a distorted octahedral geometry that is proposed to promote facile reductive elimination. Overall, this study represents a rare example of aerobic oxidation of an organometallic PdII precursor that leads to a well-defined PdIV species, which undergoes selective C–C bond formation under ambient conditions.
