Coordination Chemistry of Rh(III) Porphyrins: Complexes with Hydrazine, Disulfide, and Diselenide Bridging Ligands

Rh(III) porphyrin complexes with bridging hydrazine and substituted hydrazine ligands were characterized in
solution by 1H NMR spectroscopy and in the solid state by X-ray diffraction. Addition of further ligand to these
species afforded 1:1 complexes in which methylhydrazine and N,N-dimethylhydrazine preferentially bound to
the Rh center through the substituted nitrogen atom, as evidenced by 1H NMR chemical shifts. An alkylated
Rh(III) porphyrin was isolated as a decomposition product of the reaction of N,N-dimethylhydrazine with Rh(III)
porphyrin in the presence of light and oxygen. Me2Se2 and Me2S2 formed bridging and nonbridging complexes
with Rh(III) porphyrin, analogous to that observed with N,N‘-dimethylhydrazine.