A Germylene/Borane Lewis Pair and the Remarkable C=O Bond Cleavage Reaction toward Isocyanate and Ketone Molecules

作者：Li, Jiancheng; Li, Bin; Liu, Rui; Jiang, Liuyin; Zhu, Hongping^*; Roesky, Herbert W.^*; Dutta, Sayan; Koley, Debasis^*; Liu, Weiping; Ye, Qingsong

来源：Chemistry - A European Journal, 2016, 22(41): 14499-14503.

DOI：10.1002/chem.201603544

• C=O bond cleavage
• coordination chemistry
• density functional calculations
• germylene
• borane Lewis pairs
• isonitrile

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.

• 出版日期2016-10
• 单位厦门大学; 昆明贵金属研究所