Carbene-Bound Borane and Silane Adducts: A Comprehensive DFT Study on Their Stability and Propensity for Hydride-Mediated Ring Expansion

被引：71

作者：

Momeni, Mohammad R. ^{[1
]}

Rivard, Eric ^{[1
]}

Brown, Alex ^{[1
]}

机构：

[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 21期

基金：

加拿大自然科学与工程研究理事会;

关键词：

N-HETEROCYCLIC CARBENES; CORRELATED MOLECULAR CALCULATIONS; POLARIZABLE CONTINUUM MODEL; GAUSSIAN-BASIS SETS; ELECTRONIC-STRUCTURE; BOND ACTIVATION; MAIN-GROUP; B-H; CYANOSILYLATION; COMPLEXES;

D O I：

10.1021/om400791r

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The stability of a variety of borane (BH3 and BH2NHMe) and silane (SiHnPh4-n, n = 0-4) adducts with diamino (NHC) and aminoalkyl (CAAC) carbenes has been carefully examined using M06-2X/cc-pVDZ computations, including natural bond orbital and atoms-in-molecules analyses. Moreover a potential mechanism for the hydride-mediated ring expansion of the carbene donors is reported. While the NHC adducts can undergo thermally induced ring-expansion chemistry, the CAAC adducts show increased stability due to a large energetic barrier for the insertion of boron (or silicon) atoms into the CAAC heterocycle. A series of substituted NHCs were investigated to further explore the roles of both electronic and steric effects on adduct stabilities and on their propensities for undergoing ring-expansion transformations.

引用

页码：6201 / 6208

页数：8

共 57 条

[31] Accurate reaction paths using a Hessian based predictor-corrector integrator [J].

Hratchian, HP ;

Schlegel, HB .

JOURNAL OF CHEMICAL PHYSICS, 2004, 120 (21) :9918-9924

[32] A theoretical study on the ring expansion of NHCs by silanes [J].

Iversen, Kalon J. ;

Wilson, David J. D. ;

Dutton, Jason L. .

DALTON TRANSACTIONS, 2013, 42 (31) :11035-11038

[33] An N-heterocyclic carbene adduct of diatomic tin, Sn=Sn [J].

Jones, Cameron ;

Sidiropoulos, Anastas ;

Holzmann, Nicole ;

Frenking, Gernot ;

Stasch, Andreas .

CHEMICAL COMMUNICATIONS, 2012, 48 (79) :9855-9857

[34]

Jones M., 2004, Reactive Intermediate Chemistry

[35] Synthesis and Characterization of a Neutral Tricoordinate Organoboron Isoelectronic with Amines [J].

Kinjo, Rei ;

Donnadieu, Bruno ;

Celik, Mehmet Ali ;

Frenking, Gernot ;

Bertrand, Guy .

SCIENCE, 2011, 333 (6042) :610-613

[36] Stable cyclic (alkyl) (amino) carbenes as rigid or flexible, bulky, electron-rich ligands for transition-metal catalysts:: A quaternary carbon atom makes the difference [J].

Lavallo, V ;

Canac, Y ;

Präsang, C ;

Donnadieu, B ;

Bertrand, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (35) :5705-5709

[37] A Stable Singlet Biradicaloid Siladicarbene: (L:)2Si [J].

Mondal, Kartik Chandra ;

Roesky, Herbert W. ;

Schwarzer, Martin C. ;

Frenking, Gernot ;

Niepoetter, Benedikt ;

Wolf, Hilke ;

Herbst-Irmer, Regine ;

Stalke, Dietmar .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (10) :2963-2967

[38] The Development and Catalytic Uses of N-Heterocyclic Carbene Gold Complexes [J].

Nolan, Steven P. .

ACCOUNTS OF CHEMICAL RESEARCH, 2011, 44 (02) :91-100

[39] A 5TH-ORDER PERTURBATION COMPARISON OF ELECTRON CORRELATION THEORIES [J].

RAGHAVACHARI, K ;

TRUCKS, GW ;

POPLE, JA ;

HEADGORDON, M .

CHEMICAL PHYSICS LETTERS, 1989, 157 (06) :479-483

[40] Catalytic activity of N-heterocyclic carbenes in ring opening polymerization of cyclic siloxanes [J].

Rodriguez, Marta ;

Marrot, Sebastien ;

Kato, Tsuyoshi ;

Sterin, Sebastien ;

Fleury, Etienne ;

Baceiredo, Antoine .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2007, 692 (04) :705-708

← 1 2 3 4 5 6 →