title: Chemical bonding in transition metal complexes with beryllium ligands [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] (M = Ni, Pd, Pt).
abstract: The equilibrium geometries and bond dissociation energies of the 14 valence electron (VE) complexes [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] with M = Ni, Pd, and Pt have been calculated using density functional theory at the BP86/TZ2P level. The nature of the M-Be bond was analyzed with the NBO charge decomposition analysis and the EDA energy decomposition analysis. The theoretical results predict the equilibrium structures with a T-shaped geometry at the transition metal where the PMe(3) ligands are in the axial positions. The calculated bond dissociation energies show that the M-E bond strengths are in the range of donor-acceptor complexes of divalent beryllium compounds with ammonia. The bond strength decreases when the substituent at beryllium changes from Cl to CH(3). The NBO analysis shows a negative charge at the BeX(2) fragment, which indicates a net charge flow from the transition metal fragment to the beryllium fragment. The energy decomposition analysis of the M-Be bonds suggests two donor-acceptor bonds with sigma and pi symmetry where the transition metal fragment is a double donor with respect to the beryllium ligand. The pi component of the [Ni]-->BeXX' donation is much smaller than the sigma component.
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany.
authors.forename: Pattiyil
authors.initials: P
authors.lastname: Parameswaran
authors.forename: Gernot
authors.initials: G
authors.lastname: Frenking
mesh_terms: D001608:Beryllium / Q000737:chemistry*; D001665:Binding Sites; D003198:Computer Simulation; D008024:Ligands; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D010984:Platinum; D010165:Palladium; D009532:Nickel; D001608:Beryllium