Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(
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- 作者：Li Yang ; Vladimir N. Nesterov ; Xiaoping Wang…
- 关键词：Osmium clusters ; Ligand substitution ; Diphosphine ligand activation ; X ; ray crystallography ; DFT
- 刊名：Journal of Cluster Science
- 出版年：2015
- 出版时间：January 2015
- 年：2015
- 卷：26
- 期：1
- 页码：93-109
- 全文大小：830 KB
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21. C. Lee, W. Yang, and - 刊物类别：Chemistry and Materials Science
- 刊物主题：Chemistry
Catalysis
Inorganic Chemistry
Physical Chemistry - 出版者：Springer Netherlands
- ISSN：1572-8862
文摘
The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(μ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373?K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C–H bonds and one P–C(phenyl) bond, to furnish the dihydride cluster H2Os3(CO)8[μ3-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3?→?strong class="a-plus-plus">5?+?2CO?+?benzene is computed to be exergonic by 12.7?kcal/mol and is entropically favored due to the release of the CO and benzene by-products.