Abstract

A new class of triarylmethane-based phosphines (L1–L4) and their Pd(II) and Rh(I) complexes were synthesized and subsequently characterized by NMR spectroscopy and X-ray diffraction analysis. The reactions of these phosphines with [PdCl(π-allyl)]2 gave the square-planar Pd(II) complexes [PdCl(π-allyl)(L)] (L = L1–L4). The treatment of [PdCl(π-allyl)(L3)] and [PdCl(π-allyl)(L4)], which have CF3-substituted triarylmethane and 9-arylfluorene moieties, respectively, with LiOtBu afforded P,C(sp3)-chelated palladacycle complexes. Reversibility between a C(sp3)–M covalent bond and a C(sp3)–H···M interaction was experimentally demonstrated using [RhCl(nbd)]2 as a Rh(I) source. The triarylmethane-monophosphines L1–L4 were applied to the Pd-catalyzed 1,4-addition of arylboronic acids to enones.

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