Binuclear half-sandwich cobalt(III) and rhodium(III) ortho-carboranedichalocogenolato complexes with ether chain-bridged bis(cyclopentadienyl) ligand

摘要

1, 1 '-( 3- Oxapentamethylene) dicyclopentadiene [ O( CH2CH2C5H5)(2)] ( 1), 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 O[CH2CH2(eta(5)- C5H4) Co(CO) I-2] (2) ( 3) and insoluble polynuclear rhodium( III) complex {O[CH2CH2(eta(5)- C5H4) RhI2](2)} (n) ( 8) were obtained from reactions of 1 with the corresponding metal fragments and they react easily with PPh3 to give binuclear metal complexes, O[CH2CH2(eta(C5H4)-C-5) Co(PPh3)I-2](2) ( 4) and O[CH2CH2(eta(5)- C5H4) Rh( PPh3)I-2] (2) ( 9), respectively. Complexes 3, 4 and 9 react with bidentate dilithium dichalcogenolato ortho- carborane to give eight binuclear half- sandwich ortho-carboranedichalcogenolato cobalt( III) and rhodium( III) complexes O[CH2CH2(eta(C5H4)-C-5) Co(PPh3)(E2C2B10H10)](2) ( E = S ( 5a) and Se ( 5b)), O[CH2CH2(eta(5)- C5H4)](2)Co-2(E2C2B10H10) ( E = S ( 6a) and Se ( 6b)), O[CH2CH2(eta(5)- C5H4) Co(E2C2B10H10)](2) ( E = S ( 7a) and Se ( 7b)) and O[CH2CH2(eta(5)- C5H4) Rh(PPh3)( E2C2B10H10)] (2) ( E = S ( 10a) and Se ( 10b)). All complexes have been characterized by elemental analyses, NMR spectra (H-1, C-13, P-31 and B-11 NMR) and IR spectroscopy. The molecular structures of 3, 5a, 6a, 6b, 9 and 10b were determined by X- ray diffractometry.