Theoretical studies of inorganic compounds. 27. Quantum chemical investigations of transition metal nitrido complexes with a TM-N-E linkage (E equals main group element)

摘要

It is reported about quantum chemical DFT calculations of various transition metal (TM) nitrido complexes which contain a TM-N-E linkage. The goal is to elucidate the nature of the TM-N-E bonding situation with modern quantum chemical tools. Five comparative investigations have been carried out. (a) Comparison of the N-donor ability in the nitrido complexes Cl3W-N-ECln where ECln = NaCl, MgCl2, AlCl3- (b) Comparative analysis of the bonding situation in Cl4W-N-X where X = Na, MgCl, AlCl2, SiCl3, PCl2, SCl, Cl. (c) Comparison of the structure and bonding in Cl5W-NPH3, Cl5W-OPH3+, Cl4W-(NPH3)(OPH3)(+). (d) Comparative analysis of the bonding situation in Cl5Ta-OPH3, Cl5W-NPH3, Cl5Re-CPH3. (e) Energy decomposition analysis of the bonding of the isolobal ligands NPH3 and Cp with WCl5. [References: 47]