Metal fragment condensation and carbon-carbon bond cleavage in reactions of [Fe3(CO)12] with internal propargyl alcohols.: Structures of the "bow tie" acetylide complexes [Fe5(CO)14(C2R)2] (R = Me or Et)

被引:14
|
作者
Brait, S
Gervasio, G
Marabello, D
Sappa, E
机构
[1] Univ Piemonte Orientale Amedeo Avogadro, Dipartimento Sci & Tecnol Avanzate, I-15100 Alessandria, Italy
[2] Univ Turin, Dipartimento Chim IFM, I-10125 Turin, Italy
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 2000年 / 06期
关键词
D O I
10.1039/a908308a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The propargyl alcohols RC2C(H)(OH)R' (R = H, R' = Et; R = Me, R' = Et; R = Et, R' = Me; R = Ph, R' = Pr-i) reacted with [Fe-3(CO)(12)] in hydrocarbon solvents to give, as the final products, binuclear "ferrole" derivatives [Fe-2(CO)(6)L-2] or [Fe-2(CO)(6)(L)(L - H2O)] [L = propargyl alcohol] in several isomers. Small amounts of tri- and penta-nuclear complexes were also obtained. In particular, when R = H or Ph trinuclear complexes [Fe-3(CO)(9)-(mu-CO)L] 1 with a "parallel" alkyne ligand could be isolated and characterized by IR and NMR spectroscopies and mass spectrometry. When R = Me or Et the "bow tie" acetylide complexes [Fe-5(CO)(14)(C2R)(2)] (R = Me 2a or Et 2b) were isolated; their structures were determined by X-ray diffraction. The complexes 2a and 2b are formed by two Fe-3 triangles sharing a common vertex: each triangle is co-ordinated in a perpendicular fashion by an acetylide fragment and the carbon of one of the acetylide ligands is bound to four iron atoms. Complexes 2 are new examples of an uncommon type of cluster framework; they are presumably formed upon condensation of metal fragments generated by triiron dodecacarbonyl and upon cleavage of a carbon-carbon bond to the alkyne triple bond. Possible formation mechanisms are discussed.
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页码:989 / 994
页数:6
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