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
收藏
页码：701 / 706
页数：6
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