Abstract
Electron-rich rhodium porphyrin alkyls (omp)RhR (R=Me, i Pr, omp=2,3,7,8,12,13,17,18-octamethoxyporphyrin dianion) were photolyzed to give the non-bridged metal–metal bonded complex Rh 2(omp) 2. Reaction of (omp)RhH with TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) also yielded Rh 2(omp) 2 quantitatively. Rh 2(omp) 2 reacted with CH 3I to produce (omp)RhMe and (omp)RhI, and with Et 3SiH to give (omp)RhSiEt 3 and (omp)RhH in 42–52% yield, respectively. Addition of Rh 2(omp) 2 with styrene yielded phenylethyl-bridged complexes, (omp)RhCH 2CH(Ph)Rh(omp). Rh 2(omp) 2 reacted with triphenylphosphine to produce the cationic and anionic Rh III species of [(omp)Rh] + and [(omp)Rh] −.
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