Adams Richard D, Kiprotich Joseph, Peryshkov Dmitry V, Wong Yuen Onn
Department of Chemistry and Biochemistry, University of South Carolina, JM Palms Ctr for GSR, Columbia, SC, 29208, USA.
Chemistry. 2016 May 4;22(19):6501-4. doi: 10.1002/chem.201601075. Epub 2016 Mar 23.
The reaction of Os3 (CO)10 (NCMe)2 with closo-o-C2 B10 H10 has yielded two interconvertible isomers Os3 (CO)9 (μ3 -4,5,9-C2 B10 H8 )(μ-H)2 (1 a) and Os3 (CO)9 (μ3 -3,4,8-C2 B10 H8 )(μ-H)2 (1 b) formed by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster. Two BH bonds of the o-C2 B10 H10 were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a/1 b mixture to yield the complex Os3 (CO)9 (μ-H)2 (μ3 -4,5,9-μ3 -7,11,12-C2 B10 H7 )Os3 (CO)9 (μ-H)3 (2) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os3 (CO)9 (μ-H)(μ3 -3,4,8-μ3 -7,11,12-C2 B10 H8 )Os3 (CO)9 (μ-H) (3) by a novel opening of the carborane cage with loss of H2 .
Os3(CO)10(NCMe)2与邻碳硼烷-o-C2B10H10反应生成了两种可相互转化的异构体Os3(CO)9(μ3-4,5,9-C2B10H8)(μ-H)2(1a)和Os3(CO)9(μ3-3,4,8-C2B10H8)(μ-H)2(1b)，它们是由Os3簇失去两个NCMe配体和一个CO配体形成的。邻碳硼烷-o-C2B10H10的两个BH键在其加成到锇簇的过程中被活化。向1a/1b混合物中加入第二个三锇簇，得到配合物Os3(CO)9(μ-H)2(μ3-4,5,9-μ3-7,11,12-C2B10H7)Os3(CO)9(μ-H)3(2)，它包含两个连接在同一个碳硼烷笼上的三锇三角形。加热时，2通过碳硼烷笼的一种新型打开方式并伴随着H2的损失转化为配合物Os3(CO)9(μ-H)(μ3-3,4,8-μ3-7,11,12-C2B10H8)Os3(CO)9(μ-H)(3)。
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