A Germylene/Borane Lewis Pair and the Remarkable C=O Bond Cleavage Reaction toward Isocyanate and Ketone Molecules |
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| Authors: | Jiancheng Li Bin Li Rui Liu Liuyin Jiang Prof?Dr Hongping Zhu Prof?Dr Herbert W Roesky Sayan Dutta Dr Debasis Koley Prof Weiping Liu Qingsong Ye |
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| Affiliation: | 1. State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P. R. China;2. Institut für Anorganische Chemie, Georg-August-Universit?t, G?ttingen, Germany;3. Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, India;4. State Key Laboratory for Platinum Group Metals, Kunming Institute of Precious Metals, Kunming, Yunnan, P. R. China |
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| Abstract: | A germylene/borane Lewis pair ( 2 ) was prepared from a 1,1‐carboboration of amidinato phenylethynylgermylene ( 1 ) by B(C6F5)3. Compound 2 reacted with iPrNCO and (4‐MeOC6H4)C(O)Me, respectively, with cleavage of the C=O double bond. In the first instance, O and iPrNC insert separately into the Ge?B bond to yield a GeBC2O‐heterocycle ( 3 ) and a GeBC3‐heterocycle ( 4 ). In the second case (4‐MeOC6H4)(Me)C inserts into the Ge?N bond of 2 while O is incorporated in the Ge?B bond to form a Ge‐centered spiroheterocycle ( 5 ). The reaction of 2 with tBuNC to give 6 , which has almost the same structure as 4 , proved the formation of the isonitrile during transformation from 2 and iPrNCO to 3 and 4 . The kinetic study of the reaction of 2 and iPrNCO gave evidence of proceeding through a GeBC3O‐heterocycle intermediate. In addition, a DFT study was performed to elucidate the reaction mechanism. |
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| Keywords: | C=O bond cleavage coordination chemistry density functional calculations germylene/borane Lewis pairs isonitrile |
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