249620-35-7Relevant academic research and scientific papers
Hydrido(carbonyl) and Hydrido(carbene) Complexes of Ruthenium
Werner, Helmut,Stueer, Wolfram,Weberndoerfer, Brigit,Wolf, Justin
, p. 1707 - 1714 (2007/10/03)
The five-coordinate compound [RuHCl(CO)(PiPr2Ph)2] (1), which was prepared from RuCl3*3H2O and PiPr2Ph in methanol in the presence of NEt3, reacts with CO and with diazoalkanes RCHN2 (R=Ph, H) to give the six-coordinate complexes [RuHCl(CO)2(PiPr2Ph)2] (4) and [RuHCl(CO)=CHR)(PiPr2Ph)2] (5, 6), respectively. If the reaction of 1 with CH2N2, which at -78 deg C affords 6, is carried out at room temperature, the ionic compound [MePiPr2Ph][RuHCl2(CO)(PiPr2Ph)2] (7) is formed. The corresponding PPN salt was obtained from 1 and [PPN]Cl. The X-ray crystal structure analysis of 7 revealed, that the anionic species [RuHCl2(CO)(PiPr2Ph)2](1-) contains the chloro ligands in cis and the phosphanes in trans disposition. The Ru=CH2 bond of compound 6 is quite labile and, therefore, the CH2 unit is easily displaced by CO or pyridine. From 1 and pyridine, an isomeric mixture of [RuHCl(CO)(py)(PiPr2Ph)2] (9a, b) is formed. Treatment of 1 with HCCR (R=H, Ph) yields the five-coordinate vinylruthenium(II) complexes [Ru(CH=CHR)Cl(CO)(PiPr2Ph)2] (12, 13) by insertion of the alkyne into the Ru-H bond. The preparation of [RuHX(CO)(PiPr2Ph)2] (X=CF3CO2, I) is also reported.
