Diphosphinoazine rhodium(III) and iridium(III) octahedral complexes

Abstract

Rhodium(III) and iridium(III) octahedral complexes of general formula [MCl 3{R 2PCH 2C(Bu t ) NN C(Bu t )CH 2PR 2}] (M = Rh, Ir; R = Ph, c-C 6H 11, Pr i , Bu t ; not all the combinations) were prepared either from the corresponding diphosphinoazines and RhCl 3 · 3H 2O or by the oxidation of previously reported bridging complexes [{MCl(1,2-η:5,6-η-CH CHCH 2CH 2CH CHCH 2CH 2)} 2{μ-R 2PCH 2C(Bu t ) NN C(Bu t )CH 2PR 2}] with chlorine-containing solvents. Depending on the steric properties of the ligands, complexes with facial or meridional configuration were obtained. Crystal and molecular structures of three facial and two meridional complexes were determined by X-ray diffraction. Hemilability of ligand in the complex fac-[RhCl 3{(C 6H 11) 2PCH 2C(Bu t ) NN C(Bu t )CH 2P(C 6H 11) 2}] consisting in reversible decoordination of the phosphine donor group in the six-membered ring was observed as the first step of isomerization between fac and mer isomers.