Influence of Noncovalent Interaction on the Nucleophilicity and Electrophilicity of Metal Centers in [MII(S2CNEt2)2] (M = Ni, Pd, Pt).

Abstract

A systematic theoretical study was performed on the electrophilic and nucleophilic properties of Group 10 square-planar metal compounds [MII(S2CNEt2)2] (M = Ni 1, Pd 2, and Pt 3) and their complexes. The nucleophilic metal center and coordinated sulfur atom in [M(S2CNEt2)2] facilitate the formation of metal-involving and conventional noncovalent bonds. The presence a heavier metal center results in a more negative electrostatic potential and a larger nucleophilicity, which in turn leads to the formation of stronger metal-involving noncovalent bonds than those formed by a lighter metal center. The NiII center was observed to display electrophilic-nucleophilic dualism with regard to noncovalent interactions, forming both a metal-involving halogen bond (Ni···I) with iodine chloride (ICl) and a semicoordination bond (Ni···N) with N-bases. The nucleophilicity and electrophilicity of the NiII center are enhanced in the ternary complexes LB···1···XCl (X = H, I; LB = NH3, NHCH2, pyridine) due to the push-pull mechanism. The N···Ni semicoordination bond exerts a push effect on the dz2 orbital of the NiII center, while the Ni···X noncovalent bond provides a symbiotic pull effect on this orbital. Furthermore, the formation of metal-involving noncovalent bonds may enhance the electrophilic ability of the PdII and PtII center, resulting in the formation of stable ternary complexes Py···2/3···XCl (X = H, I), which are characterized by M···N and M···X interactions.