Quantifying and understanding the electronic properties of N-heterocyclic carbenes

被引：912

作者：

Nelson, David J. ^{[1
]}

Nolan, Steven P. ^{[1
]}

机构：

[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland

来源：

CHEMICAL SOCIETY REVIEWS | 2013年 / 42卷 / 16期

关键词：

TRANSITION-METAL-COMPLEXES; OLEFIN METATHESIS CATALYSTS; REDUCED HETEROATOM STABILIZATION; LIGAND KNOWLEDGE-BASE; CARBON ACID PK(A); IRIDIUM COMPLEXES; NHC LIGANDS; DONOR PROPERTIES; COORDINATION CHEMISTRY; MESOIONIC CARBENES;

D O I：

10.1039/c3cs60146c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The use of N-heterocyclic carbenes (NHCs) in chemistry has developed rapidly over the past twenty years. These interesting compounds are predominantly employed in organometallic chemistry as ligands for various metal centres, and as organocatalysts able to mediate an exciting range of reactions. However, the sheer number of NHCs known in the literature can make the appropriate choice of NHC for a given application difficult. A number of metrics have been explored that allow the electronic properties of NHCs to be quantified and compared. In this review, we discuss these various metrics and what they can teach about the electronic properties of NHCs. Data for approximately three hundred NHCs are presented, obtained from a detailed survey of the literature.

引用

页码：6723 / 6753

页数：31

共 213 条

[1] Introducing Axial Chirality into Mesoionic 4,4′-Bis(1,2,3-triazole) Dicarbenes [J].

Aizpurua, Jesus M. ;

Sagartzazu-Aizpurua, Maialen ;

Monasterio, Zaira ;

Azcune, Itxaso ;

Mendicute, Claudio ;

Miranda, Jose I. ;

Garcia-Lecina, Eva ;

Altube, Ainhoa ;

Fratila, Raluca M. .

ORGANIC LETTERS, 2012, 14 (07) :1866-1868

[2] Synthesis, structure and electronic properties of N-dialkylamino-and N-alkoxy-1,2,4-triazol-3-ylidene ligands [J].

Alcarazo, M ;

Fernández, R ;

Alvarez, E ;

Lassaletta, JM .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2005, 690 (24-25) :5979-5988

[3] Imidazo[1,5-a]pyridine:: A versatile architecture for stable N-heterocyclic carbenes [J].

Alcarazo, M ;

Roseblade, SJ ;

Cowley, AR ;

Fernández, R ;

Brown, JM ;

Lassaletta, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (10) :3290-3291

[4] 1,3-bis(N,N-dialkylamino)imidazolin-2-ylidenes:: Synthesis and reactivity of a new family of stable N-heterocyclic carbenes [J].

Alcarazo, M ;

Roseblade, SJ ;

Alonso, E ;

Fernández, R ;

Alvarez, E ;

Lahoz, FJ ;

Lassaletta, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (41) :13242-13243

[5] STABLE CARBENES AS STRONG BASES [J].

ALDER, RW ;

ALLEN, PR ;

WILLIAMS, SJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (12) :1267-1268

[6] When and how do diaminocarbenes dimerize? [J].

Alder, RW ;

Blake, ME ;

Chaker, L ;

Harvey, JN ;

Paolini, F ;

Schütz, J .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (44) :5896-5911

[7] Bis(diisopropylamino)carbene [J].

Alder, RW ;

Allen, PR ;

Murray, M ;

Orpen, AG .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1996, 35 (10) :1121-1123

[8] Sterically demanding, bioxazoline-derived N-heterocyclic carbene ligands with restricted flexibility for catalysis [J].

Altenhoff, G ;

Goddard, R ;

Lehmann, CW ;

Glorius, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (46) :15195-15201

[9] Formation and stability of N-heterocyclic carbenes in water:: The carbon acid pKa of imidazollum cations in aqueous solution [J].

Amyes, TL ;

Diver, ST ;

Richard, JP ;

Rivas, FM ;

Toth, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (13) :4366-4374

[10] ELECTRON-DISTRIBUTION IN A STABLE CARBENE [J].

ARDUENGO, AJ ;

DIAS, HVR ;

DIXON, DA ;

HARLOW, RL ;

KLOOSTER, WT ;

KOETZLE, TF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (15) :6812-6822

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