Silver as an Exopolyhedral Auxiliary to the Rhenacarborane Anion [Re(CO)3(5-7,8-C2B9
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- 作者：Dianne D. Ellis ; John C. Jeffery ; Paul A. Jelliss ; Jason A. Kautz ; and F. Gordon A. Stone
- 刊名：Inorganic Chemistry
- 出版年：2001
- 出版时间：April 23, 2001
- 年：2001
- 卷：40
- 期：9
- 页码：2041 - 2050
- 全文大小：223K
- 年卷期：v.40,no.9(April 23, 2001)
- ISSN：1520-510X
文摘
The rhenacarborane salt Cs[Re(CO)3(
5-7,8-C2B9H11)] (1) has been used to synthesize the tetranuclear metalcomplex [{ReAg(
-10-H-5-7,8-C2B9H10)(CO)3}2{-Ph2P(CH2)2PPh2}] (3) where two [ReAg(-10-H-5-7,8-C2B9H10)(CO)3] fragments have been shown by X-ray crystallography to be bridged by a single 1,2-bis(diphenylphosphino)ethane ligand. Reaction of 1 with Ag[BF4] in the presence of the ligands bis- or tris(pyrazol-1-yl)methane yields the complexes [ReAg(-10-H-5-7,8-C2B9H10)(CO)3{
2-CH2(C3H3N2-1)2}] (4) or [{ReAg(-10-H-5-7,8-C2B9H10)(CO)3}2{-1,2-CH(C3H3N2-1)3}] (5), respectively. From X-ray studies, the former comprisesa Re-Ag bond bridged by the carborane cage and with the bis(pyrazol-1-yl)methane coordinating the silver(I)center in an asymmetric 2 mode. Complex 5 was unexpectedly found to contain a tris(pyrazol-1-yl)methanebridging two [ReAg(-10-H-5-7,8-C2B9H10)(CO)3] fragments in a 1,2 manner. Treatment of 1 with Ag[BF4]in the presence of 2,2'-dipyridyl and 2,2':6',2' '-terpyridyl yields [ReAg(-10-H-5-7,8-C2B9H10)(CO)3{2-(C5H4N-2)2}] (6) and [ReAg(-10-H-5-7,8-C2B9H10)(CO)3{3-C5H3N(C5H4N-2)2-2,6}] (7). The X-ray structure determination of 7 revealed an unusual pentacoordinated silver(I) center, asymmetrically ligated by a 3-2,2':6',2' '-terpyridyl molecule. The same synthetic procedure using N,N,N',N'-tetramethylethylenediamine gave a tetranuclearmetal complex [{ReAg(-10-H-5-7,8-C2B9H10)(CO)3}2{-Me2N(CH2)2NMe2}2] (8) which is believed, in thesolid state, to be bridged between the silver atoms by two of the diamine molecules. The salt 1 with Ag[BF4] inthe absence of any added ligand gave the tetrameric cluster [ReAg{-5,6,10-(H)3-5-7,8-C2B9H8}(CO)3]4 (9)where, in the solid state, four [ReAg(-10-H-5-7,8-C2B9H10)(CO)3] units are held together by long interunitB-H 
Ag bonds.
5-7,8-C2B9H11)] (1) has been used to synthesize the tetranuclear metalcomplex [{ReAg(-10-H-5-7,8-C2B9H10)(CO)3}2{-Ph2P(CH2)2PPh2}] (3) where two [ReAg(-10-H-5-7,8-C2B9H10)(CO)3] fragments have been shown by X-ray crystallography to be bridged by a single 1,2-bis(diphenylphosphino)ethane ligand. Reaction of 1 with Ag[BF4] in the presence of the ligands bis- or tris(pyrazol-1-yl)methane yields the complexes [ReAg(-10-H-5-7,8-C2B9H10)(CO)3{2-CH2(C3H3N2-1)2}] (4) or [{ReAg(-10-H-5-7,8-C2B9H10)(CO)3}2{-1,2-CH(C3H3N2-1)3}] (5), respectively. From X-ray studies, the former comprisesa Re-Ag bond bridged by the carborane cage and with the bis(pyrazol-1-yl)methane coordinating the silver(I)center in an asymmetric 2 mode. Complex 5 was unexpectedly found to contain a tris(pyrazol-1-yl)methanebridging two [ReAg(-10-H-5-7,8-C2B9H10)(CO)3] fragments in a 1,2 manner. Treatment of 1 with Ag[BF4]in the presence of 2,2'-dipyridyl and 2,2':6',2' '-terpyridyl yields [ReAg(-10-H-5-7,8-C2B9H10)(CO)3{2-(C5H4N-2)2}] (6) and [ReAg(-10-H-5-7,8-C2B9H10)(CO)3{3-C5H3N(C5H4N-2)2-2,6}] (7). The X-ray structure determination of 7 revealed an unusual pentacoordinated silver(I) center, asymmetrically ligated by a 3-2,2':6',2' '-terpyridyl molecule. The same synthetic procedure using N,N,N',N'-tetramethylethylenediamine gave a tetranuclearmetal complex [{ReAg(-10-H-5-7,8-C2B9H10)(CO)3}2{-Me2N(CH2)2NMe2}2] (8) which is believed, in thesolid state, to be bridged between the silver atoms by two of the diamine molecules. The salt 1 with Ag[BF4] inthe absence of any added ligand gave the tetrameric cluster [ReAg{-5,6,10-(H)3-5-7,8-C2B9H8}(CO)3]4 (9)where, in the solid state, four [ReAg(-10-H-5-7,8-C2B9H10)(CO)3] units are held together by long interunitB-H Ag bonds.