Rhodium porphyrin catalyzed hydrogenation of the aliphatic carbon-carbon σ-bond of [2.2]paracyclophane with water has been examined with a variety of tetraarylporphyrins and axial ligands. Mechanistic investigations show that Rh(ttp)H, which can be derived from the reaction of [Rh(ttp)] with water without a sacrificial reductant, plays an important role in promoting bimetallic reductive elimination to give the hydrogenation product.
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