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Binuclear half-sandwich cobalt(III) and rhodium(III) ortho-carboranedichalocogenolato complexes with ether chain-bridged bis(cyclopentadienyl) ligand
Authors:Hou Xiu-Feng  Liu Shu  Wang Hui  Chen Yin-Qiang  Jin Guo-Xin
Institution:Department of Chemistry and Key Lab of Molecular Engineering of Polymers of Chinese Ministry of Education, Fudan University, 200433 Shanghai, China.
Abstract:1, 1'-(3-Oxapentamethylene)dicyclopentadiene O(CH(2)CH(2)C(5)H(5))(2)], containing a flexible chain-bridged group, was synthesized by the reaction of sodium cyclopentadienide with bis(2-chloroethyl) ether through a slightly modified literature procedure. Furthermore, the binuclear cobalt(III) complex OCH(2)CH(2)(eta(5)-C(5)H(4))Co(CO)I(2)](2) and insoluble polynuclear rhodium(III) complex {OCH(2)CH(2)(eta(5)-C(5)H(4))RhI(2)](2)}(n) were obtained from reactions of with the corresponding metal fragments and they react easily with PPh(3) to give binuclear metal complexes, OCH(2)CH(2)(eta(5)-C(5)H(4))Co(PPh(3))I(2)](2) and OCH(2)CH(2)(eta(5)-C(5)H(4))Rh(PPh(3))I(2)](2), respectively. Complexes react with bidentate dilithium dichalcogenolato ortho-carborane to give eight binuclear half-sandwich ortho-carboranedichalcogenolato cobalt(III) and rhodium(III) complexes OCH(2)CH(2)(eta(5)-C(5)H(4))Co(PPh(3))(E(2)C(2)B(10)H(10))](2) (E = S and Se), OCH(2)CH(2)(eta(5)-C(5)H(4))](2)Co(2)(E(2)C(2)B(10)H(10)) (E = S and Se), OCH(2)CH(2)(eta(5)-C(5)H(4))Co(E(2)C(2)B(10)H(10))](2) (E = S and Se and OCH(2)CH(2)(eta(5)-C(5)H(4))Rh(PPh(3))(E(2)C(2)B(10)H(10))](2) (E = S and Se). All complexes have been characterized by elemental analyses, NMR spectra ((1)H, (13)C, (31)P and (11)B NMR) and IR spectroscopy. The molecular structures were determined by X-ray diffractometry.
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