title: A Germylene/Borane Lewis Pair and the Remarkable C=O Bond Cleavage Reaction toward Isocyanate and Ketone Molecules.
abstract: A germylene/borane Lewis pair (2) was prepared from a 1,1-carboboration of amidinato phenylethynylgermylene (1) by B(C6 F5 )3 . Compound 2 reacted with iPrNCO and (4-MeOC6 H4 )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 GeBC2 O-heterocycle (3) and a GeBC3 -heterocycle (4). In the second case (4-MeOC6 H4 )(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 GeBC3 O-heterocycle intermediate. In addition, a DFT study was performed to elucidate the reaction mechanism.
authors.affiliation: 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, 361005, P. R. China.
authors.forename: Jiancheng
authors.initials: J
authors.lastname: Li
authors.affiliation: 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, 361005, P. R. China.
authors.forename: Bin
authors.initials: B
authors.lastname: Li
authors.affiliation: 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, 361005, P. R. China.
authors.forename: Rui
authors.initials: R
authors.lastname: Liu
authors.affiliation: 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, 361005, P. R. China.
authors.forename: Liuyin
authors.initials: L
authors.lastname: Jiang
authors.affiliation: 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, 361005, P. R. China. hpzhu@xmu.edu.cn.
authors.forename: Hongping
authors.initials: H
authors.lastname: Zhu
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 4, 37077, Göttingen, Germany. hroesky@gwdg.de.
authors.forename: Herbert W
authors.initials: HW
authors.lastname: Roesky
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, India.
authors.forename: Sayan
authors.initials: S
authors.lastname: Dutta
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, India. koley@iiserkol.ac.in.
authors.forename: Debasis
authors.initials: D
authors.lastname: Koley
authors.affiliation: State Key Laboratory for Platinum Group Metals, Kunming Institute of Precious Metals, Kunming, Yunnan, 650106, P. R. China.
authors.forename: Weiping
authors.initials: W
authors.lastname: Liu
authors.affiliation: State Key Laboratory for Platinum Group Metals, Kunming Institute of Precious Metals, Kunming, Yunnan, 650106, P. R. China.
authors.forename: Qingsong
authors.initials: Q
authors.lastname: Ye
keywords: C=O bond cleavage; coordination chemistry; density functional calculations; germylene/borane Lewis pairs; isonitrile