Hydrido(carbonyl) and hydrido(carbene) complexes of ruthenium

The five-coordinate compound [RuHCl(CO)(PiPr(2)Ph)(2)] (1), which was prepa red from RuCl3 . 3 H2O and PiPr(2)Ph in methanol in the presence of NEt3, r eacts with CO and with diazoalkanes RCHN2 (R = Ph, H) to give the six-coord inate complexes [RuHCl(CO)(2)(PiPr(2)Ph)(2)] (4) and [RuHCl(CO)(= CHR)(PiPr (2)Ph)(2)] (5, 6), respectively. If the reaction of 1 with CH2N2; which at -78 degrees C affords 6, is carried out at room temperature, the ionic comp ound [MePiPr(2)Ph][RuHCl2(CO)(PiPr(2)Ph)(2)] (7) is formed. The correspondi ng PPN salt was obtained from 1 and [PPN]Cl. The X-ray crystal structure an alysis of 7 revealed, that the anionic species [RuHCl2(CO)(PiPr(2)Ph)(2)](- ) contains the chloro ligands in cis and the phosphanes in trans dispositio n. The Ru = CH2 bond of compound 6 is quite labile and therefore, the CH2 u nit is easily displaced by CO or pyridine. From 1 and pyridine, an isomeric mixture of [RuHCl(CO)(py)(PiPr(2)Ph)(2)] (9a, b) is formed. Treatment of 1 with HC equivalent to CR (R = H, Ph) yields the five-coordinate vinylruthe nium(II) complexes [Ru(CH = CHR)Cl(CO)(PiPr(2)Ph)(2)] (12, 13) by insertion of the alkyne into the Ru - H bond. The preparation of [RuHX(CO)(PiPr(2)Ph )(2)] (X = CF3CO2, I) is also reported.