Synthesis of Iminoboryl o-Carboranes by Lewis Base Promoted Aminoborirane-to-Iminoborane Isomerization

Wang, Junyi1,2; Jia, Penghui1; Sun, Weicheng1; Wei, Yuxiang1; Lin, Zhenyang2; Ye, Qing1,3,4

2022-06-13

10.1021/acs.inorgchem.2c00944

INORGANIC CHEMISTRY   Impact Factor & Quartile

0020-1669

1520-510X

The iminoboryl o-carboranes (Me3Si)-Cb-Bsuccessfully synthesized by tetrahydrofuran (THF)-promoted isomerization from the corresponding o-carborane-fused aminoboriranes Cb{BN(SiMe3)R} (2). The synthetic protocol of the previously reported borirane 2a was optimized. The borirane Cb{BN(SiMe3)tBu} (2b) and the iminoboranes 3a and 3b were fully characterized by NMR, IR, and single-crystal X-ray diffraction analyses. The borirane 2a isomerizes more readily than 2b. The kinetics study revealed a bimolecular mechanism between borirane and THF, which is in good agreement with the computationally proposed reaction pathway. The title compounds are thermally robust, but compound 3a dimerized in the presence of a catalytic amount of tBuNC to give the cyclodimer 4. Quick equilibrium between 4 and the isonitrile adduct 4middottBuNC was observed in solution.

SCI ; EI

English

NI Journal Papers

First ; Corresponding

NSFC[22071095] ; National Young Talents Program, Technology Innovation Commission of Shenzhen Municipality[20200925152822004] ; Research Grants Council of Hong Kong[16305119]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000813649800001

AMER CHEMICAL SOC

20222512241962

Isomers ; Organic solvents ; Reaction kinetics ; Silicon ; Silicon compounds ; Single crystals ; X ray diffraction analysis

Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Crystalline Solids:933.1

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong 999077, Peoples R China
3.Julius Maximilians Univ Wurzburg, Inst Inorgan Chem, D-97074 Wurzburg, Germany
4.Julius Maximilians Univ Wurzburg, Inst Sustainable Chem & Catalysis Boron, D-97074 Wurzburg, Germany

Wang, Junyi,Jia, Penghui,Sun, Weicheng,et al. Synthesis of Iminoboryl o-Carboranes by Lewis Base Promoted Aminoborirane-to-Iminoborane Isomerization[J]. INORGANIC CHEMISTRY,2022,61(23):8879-8886.

Wang, Junyi,Jia, Penghui,Sun, Weicheng,Wei, Yuxiang,Lin, Zhenyang,&Ye, Qing.(2022).Synthesis of Iminoboryl o-Carboranes by Lewis Base Promoted Aminoborirane-to-Iminoborane Isomerization.INORGANIC CHEMISTRY,61(23),8879-8886.

Wang, Junyi,et al."Synthesis of Iminoboryl o-Carboranes by Lewis Base Promoted Aminoborirane-to-Iminoborane Isomerization".INORGANIC CHEMISTRY 61.23(2022):8879-8886.