Silyl ligand mediated reversible β-hydrogen elimination and hydrometalation at palladium
1Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8551 (Japan), Fax: (+81) 3-5734-2931.
Abstract:
The mechanism and origin of the facile β-hydrogen elimination and hydrometalation of a palladium complex bearing a phenylene-bridged PSiP pincer ligand are clarified. Experimental and theoretical studies demonstrate a new mechanism for β-hydrogen elimination and hydrometalation mediated by a silyl ligand at palladium, which enables direct interconversion between an ethylpalladium(II) complex and an η(2) -(Si-H)palladium(0) complex without formation of a square-planar palladium(II) hydride intermediate. The flexibility of the PSiP pincer ligand enables it to act as an efficient scaffold to deliver the hydrogen atom as a hydride ligand.
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