title: Metal-metal bonding in low-coordinate dicobalt complexes supported by phosphinoamide ligands.
abstract: Homobimetallic dicobalt complexes featuring metal centers in different coordination environments have been synthesized, and their multielectron redox chemistry has been investigated. Treatment of CoX(2) with MesNKP(i)Pr(2) leads to self-assembly of [(THF)Co(MesNP(i)Pr(2))(2)(μ-X)CoX] [X = Cl (1), I (2)], with one Co center bound to two amide donors and the other bound to two phosphine donors. Upon two-electron reduction, a ligand rearrangement occurs to generate the symmetric species (PMe(3))Co(MesNP(i)Pr(2))(2)Co(PMe(3)) (3), where each Co has an identical mixed P/N donor set. One-electron oxidation of 3 to generate a mixed valence species promotes a ligand reararrangement back to an asymmetric configuration in [(THF)Co(MesNP(i)Pr(2))(2)Co(PMe(3))][PF(6)] (4). Complexes 1-4 have been structurally characterized, and their metal-metal interactions are discussed in the context of computational results.
authors.affiliation: Department of Chemistry, Brandeis University, 415 South Street, Waltham, Massachusetts 02451, United States.
authors.forename: Ramyaa
authors.initials: R
authors.lastname: Mathialagan
authors.forename: Subramaniam
authors.initials: S
authors.lastname: Kuppuswamy
authors.forename: Alexandra T
authors.initials: AT
authors.lastname: De Denko
authors.forename: Mark W
authors.initials: MW
authors.lastname: Bezpalko
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Foxman
authors.forename: Christine M
authors.initials: CM
authors.lastname: Thomas