Abstract
A PNCNP pincer-ligated platinum(II) chloride complex [2,6-(tBu2PNH)2C6H3]PtCl (1a) was synthesized and fully characterized. Complex 1a was applied to the catalytic hydrosilylation of unsaturated carbon-heteroatom bonds. For comparison, the corresponding hydride complex [2,6-(tBu2PNH)2C6H3]PtH (1b) and the related POCOP pincer chloride complex [2,6-(tBu2PO)2C6H3]PtCl (1c) were also used to catalyze the reactions. It was found that 1a is a good catalyst for the hydrosilylation of both C═O and C═N bonds. Wide ranges of aldimines, ketimines, aldehydes, and ketones were hydrosilylated, and the expected amine or alcohol products were obtained in good to excellent yields. The reactions also feature good functional group compatibility. Complex 1a represents the most effective transition metal catalyst for the hydrosilylation of the C═N bond and is among the best transition metal catalysts for the hydrosilylation of the C═O bond. The reactions are likely catalyzed by a cationic platinum(II) species generated from complex 1a during the reactions.
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