Behavior of OsH2Cl2(PiPr3) 2 in acetonitrile: The importance of the small details

The behavior of OsH2Cl2(PiPr 3)2 (1) in acetonitrile as solvent is studied. Acetonitrile coordinates to the metal center of 1 and promotes the dihydride - dihydrogen transformation of its OsH2 unit to give the trans-Cl 2 compound OsCl2(η2-H2)(CH 2CN)(PiPr3)2 (2a), which evolves to its cis-Cl2 isomer 2b. Treatment of 1 with TIPF6 in acetonitrile leads to the PF6 salt of the cis-bis(acetonitrile) cation [OsCl(η2-H2)(CH3CN) 2-(PiPr3)2]+ (3a), which is transformed into its trans-bis(acetonitrile) isomer 3b. The addition of Et3N to the PF6 salts of 3a,b in acetonitrile gives [OsH(CH3CN)3(PiPr3) 2]PF6 (4). Reaction of 4 with 1,5-cyclooctadiene (COD) in refluxing toluene affords [OsH(COD)(CH3CN)2(P iPr2)]PF6 (5). The X-ray structures of 3b and 5 are also reported. © 2009 American Chemical Society.Financial support from the MICINN of Spain (Project No. CTQ2008-00810 and Consolider Ingenio 2010 CSD2007-00006) and the Diputación General de Aragón (E35) is acknowledged.Peer Reviewe