三芳基亚磷酸酯-连接钴(0)配合物[Co2(CO)6{P(OAr)3}2]的合成及其对苯乙炔和二苯乙炔的反应性

I. Jourdain, M. Knorr, Lukas Brieger, C. Strohmann
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引用次数: 2

摘要

双核配合物[Co2(CO)6{P(OAr)3}2] (1a, Ar = Ph;(1b, Ar = o-Tol)与PhC≡CH和PhC≡CPh反应得到双金属四面甾体[{(ArO)3P}(OC)2Co-Co(μ-RC≡CPh)(CO)2{P(OAr)3}] (3a, Ar = Ph, R = H;3b, Ar = o-Tol, R = H;3c, Ar = Ph, R = Ph;3d, Ar = o-Tol, R = Ph)。二苯乙炔的主反应伴有副反应,导致P(OAr)3配体解离形成单(亚磷酸酯)配合物[{(ArO)3P}(OC)2Co-Co(μ-PhC≡CPh)(CO)3] (2b, R = Ph;2d, R = o-Tol)。测定了1b、3a和3d的晶体结构以及单(亚磷酸盐)配合物[{(PhO)3P}(OC)2Co-Co(μ-PhC≡CPh)(CO)3] 2b的晶体结构。
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Synthesis of Tris(arylphosphite)-ligated Cobalt(0) Complexes [Co2(CO)6{P(OAr)3}2], and their Reactivity towards Phenylacetylene and Diphenylacetylene
The dinuclear complexes [Co2(CO)6{P(OAr)3}2] (1a, Ar = Ph; 1b, Ar = o-Tol) were prepared and reacted with PhC≡CH and PhC≡CPh to yield dimetallatetrahedranes [{(ArO)3P}(OC)2Co-Co(μ-RC≡CPh)(CO)2{P(OAr)3}] (3a, Ar = Ph, R = H; 3b, Ar = o-Tol, R = H; 3c, Ar = Ph, R = Ph; 3d, Ar = o-Tol, R = Ph). The main reaction of diphenylacetylene was accompanied by a side reaction, leading to the dissociation of a P(OAr)3 ligand for the formation of mono(phosphite) complexes [{(ArO)3P}(OC)2Co-Co(μ-PhC≡CPh)(CO)3] (2b, R = Ph; 2d, R = o-Tol). The crystal structures of 1b, 3a, and 3d were determined along with that of the mono(phosphite) complex [{(PhO)3P}(OC)2Co-Co(μ-PhC≡CPh)(CO)3] 2b.
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