Hydrido(carbonyl) and Hydrido(carbene) Complexes of Ruthenium

✍ Scribed by Helmut Werner; Wolfram Stüer; Birgit Weberndörfer; Justin Wolf

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 353 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199910)1999:10<1707::aid-ejic1707>3.0.co;2-y

✦ Synopsis

The five-coordinate compound [RuHCl(CO)(PiPr 2 Ph) 2 ] (1),

[RuHCl 2 (CO)(PiPr 2 Ph) 2 ] -contains the chloro ligands in cis and the phosphanes in trans disposition. The Ru=CH 2 bond which was prepared from RuCl 3 • 3 H 2 O and PiPr 2 Ph in methanol in the presence of NEt 3 , reacts with CO and with of compound 6 is quite labile and, therefore, the CH 2 unit is easily displaced by CO or pyridine. From 1 and pyridine, an diazoalkanes RCHN 2 (R = Ph, H) to give the six-coordinate complexes [RuHCl(CO) 2 (PiPr 2 Ph) 2 ] (4) and [RuHCl(CO)(= isomeric mixture of [RuHCl(CO)(py)(PiPr 2 Ph) 2 ] (9a, b) is formed. Treatment of 1 with HCϵCR (R = H, Ph) yields the CHR)(PiPr 2 Ph) 2 ] (5, 6), respectively. If the reaction of 1 with CH 2 N 2 , which at -78 °C affords 6, is carried out at room five-coordinate vinylruthenium(II) complexes [Ru(CH= CHR)Cl(CO)(PiPr 2 Ph) 2 ] (12, 13) by insertion of the alkyne temperature, the ionic compound [MePiPr 2 Ph][RuHCl 2 (CO)-(PiPr 2 Ph) 2 ] (7) is formed. The corresponding PPN salt was into the Ru-H bond. The preparation of [RuHX(CO)-(PiPr 2 Ph) 2 ] (X = CF 3 CO 2 , I) is also reported. obtained from 1 and [PPN]Cl. The X-ray crystal structure analysis of 7 revealed, that the anionic species