Metal-Metal Bonding in Low-Coordinate Dicobalt Complexes Supported by Phosphinoamide Ligands

被引：17

作者：

Mathialagan, Ramyaa ^{[1
]}

Kuppuswamy, Subramaniam ^{[1
]}

De Denko, Alexandra T. ^{[1
]}

Bezpalko, Mark W. ^{[1
]}

Foxman, Bruce M. ^{[1
]}

Thomas, Christine M. ^{[1
]}

机构：

[1] Brandeis Univ, Dept Chem, Waltham, MA 02451 USA

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 02期

关键词：

EFFECTIVE CORE POTENTIALS; RAY CRYSTAL-STRUCTURES; STRUCTURAL-CHARACTERIZATION; MOLECULAR CALCULATIONS; COBALT(II); MN; SUSCEPTIBILITY; APPROXIMATION; ACTIVATION; COMPOUND;

D O I：

10.1021/ic3018375

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Homobimetallic dicobalt complexes featuring metal centers in different coordination environments have been synthesized, and their multielectron redox chemistry has been investigated. Treatment of CoX2 with MesNkP(i)Pr(2) leads to self-assembly of [(THF)Co(MesNP(i)Pr(2))(2)(mu-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 (PMe3)Co(MesNP(i)Pr(2))(2)Co(PMe3) (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(PMe3)][PF6] (4). Complexes 1-4 have been structurally characterized, and their metal-metal interactions are discussed in the context of computational results.

引用

页码：701 / 706

页数：6

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