期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 37, 页码 11597-11603出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201201558
关键词
isoosmabenzene; metallacycles; nucleophilic addition; osmabenzyne; osmium
资金
- National Natural Science Foundation of China [20925208, 21103142]
- National Basic Research Program of China (973 Program) [2012CB821600]
We report herein the first example of the conversion of metallabenzyne II and isometallabenzene III. The osmium hydride vinylidene complex 1 reacts with HC?CCH(OEt)2 to give osmabenzyne 3 via isoosmabenzene 2. Compound 3 exhibits high thermal stability in air. Nonetheless, nucleophilic attack at 3 provides isoosmabenzenes 4?a and 4?b, or opens the ring to produce 5?a and 5?b. We propose mechanisms to disclose the intrinsic connection between the six-membered metallacycles, and carry out DFT calculations to rationalize the regioselectivity of the nucleophilic addition reactions.
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