Synthesis, molecular structure and reactions of stable square-planar 16-electron ruthenium(0) complexes: Trans-[RuCl(NO)(PR3)2]

Article abstract of DOI:10.1002/cber.19961290906

The reduction of [RuCl₃(NO)(PPh₃)₂] (1) with Zn/Cu generates [RuCl(NO)(PPh₃)₂] that by ligand exchange with PR₃ (R₃ = iPr₃, iPr₂Ph) affords the stable 16-electron ruthenium(0) complexes trans-[RuCl(NO)(PR₃)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)(PR₃)₂] (4, 5). On treatment of 2 and 3 with CO, TCNE, CH₂ (generated from CH₂N₂) and O₂, five-coordinate 1:1 adducts [RuCl(NO)(L)(PR₃)₂] (6-12) are formed. The dioxygen complexes 11 and 12 react with SO₂ to afford the sulfatoruthenium(II) derivatives [RuCl(NO){η²(O,O)-O₂SO₂}(PR ₃)₂] (13, 14). Compound 13 (R₃ = PiPr₃) has been characterized by X-ray structural analysis. VCH Verlagsgesellschaft mbH, 1996.