Seven-Coordinate Ruthenium Complex with an SiNN-Pincer Ligand as a Catalyst for Vinyl C─H Deuteration of Olefins

具有 SiNN 钳形配体的七配位钌配合物作为烯烃乙烯基 C─H 氘代反应的催化剂

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Abstract

Seven-coordinate ruthenium complexes 1a and 1b, featuring silyl-2,2´-bipyridine SiNN-pincer ligands with i-Pr and t-Bu groups on Si, respectively, were synthesized. Their capped octahedral structures were revealed by single-crystal X-ray diffraction study. The stoichiometric reactions of 1a and 1b with styrene in THF afforded η(2)-silylalkene chelate complexes. In contrast, performing the same reaction using 1a in C(6)D(6) resulted in the liberation of deuterated styrene (PhDC═CD(2)), alongside the formation of a deuterated η(2)-silylalkene complex. Complex 1a exhibited efficient catalytic activity for the triple deuteration of vinyl hydrogens in mono-substituted olefins with C(6)D(6) to afford RDC═CD(2) (R = Ph, C(6)H(4)-4-OMe, t-Bu) with high deuterium incorporation (92%-99%D).

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