Rhodium-Induced Reversible C-C Bond Cleavage: Transformations of Rhodium(III) 22-Alkyl-m-benziporphyrins

The structurally prearranged carbaporphyrins 22-methyl- and 22-ethyl-m-benziporphyrins provide the platform stabilizing aromatic rhodium(III) 22-(mu-methylene-m-benziporphyrin) and rhodium(III) 22-(mu-ethylidene-m-benziporphyrin). An intramolecular conversion facilitated by the m-phenylene reactivity and observed for both aromatic complexes efficiently leads to rhodium(III) 21-(mu-methylene)-21-carbaporphyrin and rhodium(III) 21-(mu-ethylidene)-21-carbaporphyrin. The distinctive macrocyclic environment of rhodium(III) 21-carbaporphyrin created an opportunity to trap unique organometallic transformations of inner core substituents affording the fulvene-like bond pattern or the rearrangement to 21-vinyl substituent. The one-electron reduction of the rhodium(III) carbaporphyrin anion pi-radical with a (d(xy))(2)(d(xz))(2)(d(yz))(2)-(P center dot-) electronic configuration is demonstrated. The further process of reduction of paramagnetic species triggers the ethyl migration from carbon(22) to rhodium(III), affording the diamagnetic rhodium(III) meta-benziporphyrin containing the apically coordinated sigma-ethyl ligand providing an example of reversible C(sp(2))-C(sp(3)) bond cleavage.