Heterooctanuclear Cluster Complex Formation with Phosphine Participation: Synthesis, Structure, and Magnetic Properties of Co6Ru2(mp)10(PBun3)
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- 作者：Zhong-Ning Chen ; Wen-Jie Li ; Bei-Sheng Kang ; Mao-Chun Hong ; Zhong-Yuan Zhou ; Thomas C. W. Mak ; Zhang Lin ; Xiao-Ming Chen ; and Han-Qin Liu
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：January 15, 1997
- 年：1997
- 卷：36
- 期：2
- 页码：208 - 213
- 全文大小：189K
- 年卷期：v.36,no.2(January 15, 1997)
- ISSN：1520-510X
文摘
The reaction of CoCl2, RuCl3,Na2(mp), and PBun3(H2mp = 2-mercaptophenol,PBun3 =tri-n-butylphosphine)in ethanol in the molar ratio of 0.75:0.25:1:1 gave the complexCo6Ru2(mp)10(PBun3)6.The heterooctanuclearcomplex consists of six cobalt and two ruthenium ions chelated to aswell as bridged by the 2-mercaptophenolligands in a near-dimeric fashion with two 
2-OR groupsbridging the twoCo3Ru(mp)5(PBun3)3fragments withouta crystallographic center of symmetry. Each fragment is formed bybinding two of theCo(mp)2(PBun3)structuralunits and one Co(mp) species to a central Ru(III) ion throughthe S donors of the five mp ligands, while the sixthcoordination site of the octahedral Ru environment is completed by aphosphine ligand in the axial position. TheCo6Ru2 moiety exhibits a zigzag assemblyconstructed by the 2-O and 2-S bridges ofthe bidentate2-mercaptophenol ligands in a highly asymmetric fashion. The Coatoms are square pyramidally coordinatedwith apices that are occupied by the phosphine ligands or an oxygenatom from a mp2- ligand.Variable-temperaturemagnetic susceptibilities that were measured in the temperature range300-1.6 K reveal that the spin clusterexhibits weak antiferromagnetic exchange interactions. Aquantitative interpretation of the magnetic data wascarried out by the irreducible tensor operator approach. Crystaldata of the complex are as follows: triclinicspace group P
, a = 14.931(3) Å,b = 23.195(5) Å, c = 24.259(5) Å,
= 74.91(3)
, 
= 74.83(3), 
=78.80(3), and Z = 2.
2-OR groupsbridging the twoCo3Ru(mp)5(PBun3)3fragments withouta crystallographic center of symmetry. Each fragment is formed bybinding two of theCo(mp)2(PBun3)structuralunits and one Co(mp) species to a central Ru(III) ion throughthe S donors of the five mp ligands, while the sixthcoordination site of the octahedral Ru environment is completed by aphosphine ligand in the axial position. TheCo6Ru2 moiety exhibits a zigzag assemblyconstructed by the 2-O and 2-S bridges ofthe bidentate2-mercaptophenol ligands in a highly asymmetric fashion. The Coatoms are square pyramidally coordinatedwith apices that are occupied by the phosphine ligands or an oxygenatom from a mp2- ligand.Variable-temperaturemagnetic susceptibilities that were measured in the temperature range300-1.6 K reveal that the spin clusterexhibits weak antiferromagnetic exchange interactions. Aquantitative interpretation of the magnetic data wascarried out by the irreducible tensor operator approach. Crystaldata of the complex are as follows: triclinicspace group P, a = 14.931(3) Å,b = 23.195(5) Å, c = 24.259(5) Å, = 74.91(3), = 74.83(3), =78.80(3), and Z = 2.