Osmium-Antimony Higher Nuclearity Clusters
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- 作者：Weng Kee Leong and Guizhu Chen
- 刊名：Organometallics
- 出版年：2001
- 出版时间：May 28, 2001
- 年：2001
- 卷：20
- 期：11
- 页码：2280 - 2287
- 全文大小：155K
- 年卷期：v.20,no.11(May 28, 2001)
- ISSN：1520-6041
文摘
Thermolysis of Os3(CO)11(SbPh3), 1, in refluxing octane gave initially the clusters Os3(
-SbPh2)(-H)(3,
2-C6H4)(CO)9, 2, and Os6(3-SbPh)(3,2-C6H4)(CO)20, 3. Prolonged heatinggave the cluster Os6(4-Sb)(-H)(3,4-C12H8)(3,2-C6H4)(CO)16, 4, as the major product. Incontrast, thermolysis in hexane at 115 
C in a Carius tube gave Os6(4-Sb)(-SbPh2)(-H)2(3,4-C12H8)(3,2-C6H4)(CO)15, 5, Os6(4-Sb)(-SbPh2)(-H)(3,2-C6H4)2(C6H5)(CO)16, 6, andOs6(4-Sb)(-SbPh2)(-H)(3,6-C6H4)(3,2-C6H4)(C6H5)(CO)15, 7, besides 2 and 3. It has beendemonstrated that cluster 6 was formed from 2, while clusters 5 and 7 were formed fromthe further decomposition of 6. The reaction of 5 with SbPh3 afforded a monosubstitutedderivative, Os6(4-Sb)(-H)2(-SbPh2)(3,2-C6H4)(3,4-C12H8)(CO)14(SbPh3), 8. The clusters2-8 were all shown by single-crystal X-ray crystallographic studies to have a benzyne moietyacting as a four-electron donor to a triosmium fragment. In addition, 4 and 8 contain anovel 3,4-biphenylene moiety bound to a triosmium framework, while 7 was found to havea 3,1:1:6-C6H4 ring.
-SbPh2)(-H)(3,2-C6H4)(CO)9, 2, and Os6(3-SbPh)(3,2-C6H4)(CO)20, 3. Prolonged heatinggave the cluster Os6(4-Sb)(-H)(3,4-C12H8)(3,2-C6H4)(CO)16, 4, as the major product. Incontrast, thermolysis in hexane at 115 C in a Carius tube gave Os6(4-Sb)(-SbPh2)(-H)2(3,4-C12H8)(3,2-C6H4)(CO)15, 5, Os6(4-Sb)(-SbPh2)(-H)(3,2-C6H4)2(C6H5)(CO)16, 6, andOs6(4-Sb)(-SbPh2)(-H)(3,6-C6H4)(3,2-C6H4)(C6H5)(CO)15, 7, besides 2 and 3. It has beendemonstrated that cluster 6 was formed from 2, while clusters 5 and 7 were formed fromthe further decomposition of 6. The reaction of 5 with SbPh3 afforded a monosubstitutedderivative, Os6(4-Sb)(-H)2(-SbPh2)(3,2-C6H4)(3,4-C12H8)(CO)14(SbPh3), 8. The clusters2-8 were all shown by single-crystal X-ray crystallographic studies to have a benzyne moietyacting as a four-electron donor to a triosmium fragment. In addition, 4 and 8 contain anovel 3,4-biphenylene moiety bound to a triosmium framework, while 7 was found to havea 3,1:1:6-C6H4 ring.