C,N-Chelated (2-Pyridylmethyl)rhodium(III) Complexes and a Novel Dinuclear Rhodium(III) Complex Containing a 2,6-Dimethylpyridine-α,α'-diyl Group as an η2(C,N):η3(C,C',N)-Bridging Ligand

Article abstract of DOI:10.1246/bcsj.68.183

Oxidative-addition reactions of excess 2-(chloromethyl) and 2,6-bis(chloromethyl)pyridines with in toluene at room temperature afforded (2-pyridylmethyl)- and <2-(6-chloromethyl)pyridylmethyl>rhodium(III) complexes, cis(PP)-(PPh3)2> (R=H, 1-cis; R=CH2Cl, 2-cis), respectively, which isomerized to the corresponding trans(PP) complexes at elevated temperature.In refluxing toluene, the reactions thus resulted in the trans(PP) complexes (R=H, 1-trans; R=CH2Cl, 2-trans) exclusively.A novel dinuclear rhodium(III) complex )PPh3)2>, in which the 2,6-dimethylpyridine-α,α'-diyl ligand is C,N-chelated to one rhodium atom and bound to the second one in an η³-pseudo-1-azaalkylic fashion, was obtained by reactions of 2,6-bis(chloromethyl)pyridine with (1:2 in mole) and of the 2-cis with (1:1 in mole), both in refluxing toluene.These were characterized by 1H, 13C, and 31P NMR spectroscopy and mass spectrometry as well as an elemental analysis and a molecular-weight determination.