Substituted boat-shaped Co6 carbonyl cluster derivatives containing a semi-interstitial P atom and both bridging dithiolate and heterocyclic phosphido ligands

Autor: Ying-Chun Liu, Zhi-Rong Zhao, Shu-Tang Liu, Bin-Fang Wu, Xiang Hu, Er-Run Ding, Fei Chang
Rok vydání: 2002
Předmět:
Zdroj: Polyhedron. 21:1073-1080
ISSN: 0277-5387
DOI: 10.1016/s0277-5387(02)00855-0
Popis: The reaction of Co2(CO)8 with Cl PSCH 2 CH 2 CH 2 S gives the Co6 cluster Co6(μ6-P)(μ-SCH2CH2CH2S)(μ- PSCH 2 CH 2 CH 2 S )(CO)12 (5). X-ray structural analysis of 5 revealed that six Co atoms form a boat-shaped array consisting of a basal square of four cobalt atoms with two opposite edges bridged by two apical Co atoms, a semi-interstitial P atom, a propanedithiolate ligand doubly bridging a basal side and a heterocyclic phosphido ligand bridging the opposite basal edge. Reaction of 5 with PPh3 results in the formation of the mono-substituted products (Co6(μ6-P)(μ-SCH2CH2CH2S)(μ- PSCH 2 CH 2 CH 2 S )(μ-CO)(CO)10(PPh3) (6) and (Co6(μ6-P)(μ-SCH2CH2CH2S)(μ- PSCH 2 CH 2 CH 2 S )(μ-CO)(CO)11(PPh3) (7). Reaction of (Co6(μ6-P)(μ-SCH2CH2S)(μ- PSCH 2 CH 2 S )(CO)12 (4) with PPh3 at higher temperature results in the formation of the di-substituted cluster Co6(μ6-P)(μ-SCH2CH2S)(μ- PSCH 2 CH 2 S )(CO)10·(PPh3)2 (8). Reactions of 5 with P(OEt)3 result in the substitution of one or two carbonyl groups to give (Co6(μ6-P)(μ-SCH2CH2CH2S)(μ- PSCH 2 CH 2 CH 2 S )(CO)11P(OEt)3)} (9) and {Co6(μ6-P)(μ-SCH2CH2CH2S)(μ- PSCH 2 CH 2 CH 2 S )(CO)11(P(OEt)3)} (9′) with different spectral data from that of (9), and {Co6(μ6-P)(μ-SCH2CH2CH2S)(μ- PSCH 2 CH 2 CH 2 S )(μ-CO)(CO)9(P(OEt)3)2} (10). X-ray structural analysis of 10 identified the sites of phosphite substitution as the two apical Co atoms. A semi-bridging CO group in 10 is located on a basal side. The IR ν(CO) solution spectrum of 10 does indicate the existence of the semi-bridging CO group in the solution as well.
Databáze: OpenAIRE
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