Synthesis, molecular structure and reactions of stable square-planar 16-electron ruthenium(0) complexes: Trans-[RuCl(NO)(PR(3))2]

The reduction of [RuCl3(NO)(PPh(3))(2)] (1) with Zn/Cu generates [RuCl(NO)(PPh(3))(2)] that by ligand exchange with PR(3) (R(3) = iPr(3), iPr(2)Ph) affords the stable PB-electron ruthenium(0) complexes trans-[RuCl(NO)(PR(3))(2)] (2, 3) The X-ray structural analysis of 2 confirmed the square-planar geometry around the metal center. HCl oxidatively adds to 2 and 3 to give the octahedral ruthenium(II) compounds [RuHCl2-(NO)(PR(3))(2)] (4, 5). On treatment of 2 and 3 with CO, TCNE, CH2 (generated from CH2N2) and O-2, five-coordinate 1:1 adducts [RuCl(NO)(L)(PR(3))(2)] (6-12) are formed. The dioxygen complexes 11 and 12 react with SO2 to afford the sulfatoruthenium(ll) derivatives [RuCl(NO){eta(2)(O,O)-O2SO2} (PR(3))(2)] (13, 14). Compound 13 (R(3) = PiPr(3)) has been characterized by X-ray structural analysis.