화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.113, No.16, 4534-4548, 2009
Noncovalent Interactions of Ni+ with N-Donor Ligands (Pyridine, 4,4'-Dipyridyl, 2,2'-Dipyridyl, and 1,10-Phenanthroline): Collision-Induced Dissociation and Theoretical Studies
Kinetic-energy-dependent collision-induced dissociation (CID) of complexes of a variety of N-donor ligands (N-L) with Ni+, Ni+(N-L)(x), is studied using guided ion beam tandem mass spectrometry. The N-donor ligands investigated include: pyridine, 4,4'-dipyridyl, 2,2'-dipyridyl, and 1,0-phenanthroline. For most of the Ni+(N-L)(x) complexes, CID results in endothermic loss of a single neutral N-L ligand as the primary dissociation pathway. Sequential dissociation of additional N-L ligands is observed at elevated energies for the pyridine and 4,4'-dipyridyl complexes containing more than one ligand. The cross-section thresholds for the primary dissociation pathways are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) of the Ni+(N-L, complexes after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and their lifetimes for dissociation. Density functional theory calculations at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level are performed to obtain model structures, molecular parameters, and energetics for the neutral N-L ligands and the Ni+(N-L)(x) complexes. In general, theory is found to overestimate the strength of binding to the first N-L ligand, and underestimate the strength of binding to additional ligands. Trends in the sequential BDEs of the Ni+(N-L)(x) complexes are examined and compared to complexes of Nil, to several other ligands previously investigated. The trends in the sequential BDEs are primarily determined by the valence electronic configuration and the effects of sd-hybridization of Ni+ but are also influenced by repulsive ligand-ligand interactions. Natural bond orbital analyses indicate that the binding in these complexes is primarily noncovalent.