Classical hydroformylation catalysts use mononuclear rhodium(I) complexes as precursors; however, very few examples of bimetallic systems have been reported. Herein, we report fully substituted dirhodium(II,II) complexes (-) containing acetate and diphenylformamidinate bridging ligands (-). The structure and geometry around these paddlewheel-type, bimetallic cores were confirmed by single-crystal X-ray diffraction. The complexes - show electrochemical redox reactions, with the expected reduction (Rh) and two oxidation (Rh and Rh) electron transfer processes. Furthermore, the bimetallic complexes were evaluated as catalyst precursors for the hydroformylation of 1-octene, with the acetate-containing complexes ( and ) showing near quantitative conversion (>99%) of 1-octene, excellent activity and chemoselectivity toward aldehydes (>98%), with moderate regioselectivity toward linear products. Replacement of the acetate with diphenylformamidinate ligands (complexes -) yielded moderate-to-good chemoselectivity and regioselectivity, favoring linear aldehydes.
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