Synthesis and structures of the dinuclear nitrido complexes [(Me2PhP)(3)(MeCN)ClRe N-MCl5] with M = Sn and Zr

The water sensitive complexes [(Me2PhP)(3)(MeCN)ClRe=N-MCl5] (M = Sn (1) an d Zr (2)) are obtained in dichloromethane from [ReNCl2(PMe2Ph)(3)] and the acetonitrile adducts of SnCl4 or ZrCl4. The compounds crystallize as dichlo romethane solvate isotypically with [(Me2PhP)(3)(MeCN)ClRe=N-TiCl5] CH2Cl2 in the space group P2(1)/n. From toluene crystallize monoclinic crystals of 1 MeCN C7H8 In the diamagnetic complexes 1 and 2 an anion [MCl5](-) coordi nates to the nitrido ligand of the cationic complex [ReNCl(MeCN)(PMe(2)h)(3 )](+). The resulting nitrido bridges Re=N-M are almost linear and asymmetri c with Re-N=169.5 pm, Sn-N = 230.1 pm and Re-N-Sn = 164.5 degrees for 1 and Re-N = 168.4 pm, Zr-N = 237.2 pm and Re-N-Zr = 165.6 degrees for 2. The ph osphine ligands at the Re atom are in a meridional arrangement.