American Chemical Society
ic2c03778_si_001.pdf (1.16 MB)

π Acceptor Abilities of Anionic Ligands: Comparisons Involving Anionic Ligands Incorporated into Linear d10 [(NH3)Pd(A)], Square Planar d8 [(NN2)Ru(A)], and Octahedral d6 [(AsN4)Tc(A)] Complexes

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journal contribution
posted on 2023-05-17, 13:33 authored by Thomas M. Gilbert
Extended transition state-natural orbitals for chemical valence (ETS-NOCV)] data were used to rank electron acceptor capacities for several potentially synergistic anionic ligands incorporated into linear d10 [(NH3)Pd(A)], square planar d8 [(NN2)Ru(A)], and octahedral d6 [(AsN4)Tc(A)] complexes [A = anionic ligand, NN2 = HN(CH2CH2CH2NH2)2, and AsN4 = [As(CH2CH2CH2NH2)4]]. It was possible to differentiate between the best acceptors, among them BI2 and B(CF3)2, and the poorest ones. A sizable fraction of the anionic ligands studied exhibit similar acceptor capacities (backbonding), mostly regardless of d electron count. A number of trends were discerned, including the fact that acceptor capacity decreases down families and across rows but increases down families of the peripheral substituents. The latter appears tied to the ability of the peripheral ligands to compete with the metal in donating electrons to the ligand-binding atom.