Abstract: | 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 ) und Zr ( 2 )) are obtained in dichloromethane from ReNCl2(PMe2Ph)3] and the acetonitrile adducts of SnCl4 or ZrCl4. The compounds crystallize as dichloromethane solvate isotypically with (Me2PhP)3(MeCN)ClRe≡N–TiCl5] · CH2Cl2 in the space group P21/n. From toluene crystallize monoclinic crystals of 1 · MeCN · C7H8. In the diamagnetic complexes 1 and 2 an anion MCl5]– coordinates to the nitrido ligand of the cationic complex ReNCl(MeCN)(PMe2Ph)3]+. The resulting nitrido bridges Re≡N–M are almost linear and asymmetric with Re–N = 169.5 pm, Sn–N = 230.1 pm and Re–N–Sn = 164.5° for 1 and Re–N = 168.4 pm, Zr–N = 237.2 pm and Re–N–Zr = 165.6° for 2 . The phosphine ligands at the Re atom are in a meridional arrangement. |