Silyl Ligand Mediated Reversible β‐Hydrogen Elimination and Hydrometalation at Palladium |
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| Authors: | Dr. Jun Takaya Prof. Dr. Nobuharu Iwasawa |
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| Affiliation: | Department of Chemistry, Tokyo Institute of Technology, O‐okayama, Meguro‐ku, Tokyo, 152‐8551 (Japan), Fax: (+81)?3‐5734‐2931 |
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| 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 η2‐(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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| Keywords: | hydride ligands ligand effects palladium reaction mechanisms silicon |
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