Dinitrogen extrusion from diazidophenylborane:: Computational analysis of PhBNx (x=6,4,2) isomers

被引：3

作者：

Bettinger, Holger F. ^{[1
]}

机构：

[1] Ruhr Univ Bochum, Lehrstuhl Organ Chem 2, D-44780 Bochum, Germany

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2006年 / 691卷 / 21期

关键词：

density functional theory computations; azido boranes; reactive intermediates; borylene; DEGENERATE PERTURBATION-THEORY; BORON; BCL(N-3)(2); PHOTOLYSIS; SPECTRA; DENSITY; SINGLET; AZIDES;

D O I：

10.1016/j.jorganchem.2006.01.017

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The energies and structures of possible intermediates in the dinitrogen extrusion from diazidophenylborane 4a to give phenylborylene 11a were determined using density functional (B3LYP), multiconfigurational (CASSCF and MRMP2), and coupled cluster (CCSD(T)) computations in conjunction with basis sets of up to cc-pVTZ quality. Formation of 11a and nitrogen from 4a is an exothermic process (-21 kcal mol(-1)). The triplet electronic ground state of azidophenylborylnitrene 5a (PhBN4) is only 26 kcal mol(-1) higher in energy than 4a and the phenyl shift in 5a to yield N-azidophenyliminoborane 7a is highly exothermic. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：4480 / 4485

页数：6

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