Tuning steric and electronic effects in transition-metal β-diketiminate complexes

被引:130
作者
Chen, Chi [1 ]
Bellows, Sarina M. [2 ]
Holland, Patrick L. [1 ]
机构
[1] Yale Univ, Dept Chem, New Haven, CT 06511 USA
[2] Univ Rochester, Dept Chem, Rochester, NY 14627 USA
基金
美国国家科学基金会; 美国国家卫生研究院;
关键词
CATALYTIC NITRENE TRANSFER; BOND-CLEAVAGE; ALKYL COMPLEXES; DIALKYLSCANDIUM COMPLEXES; VINYL POLYMERIZATION; DIOXYGEN ACTIVATION; CRYSTAL-STRUCTURES; CU(II) COMPLEXES; ARENE EXCHANGE; ATOM-TRANSFER;
D O I
10.1039/c5dt02215k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
beta-Diketiminates are widely used supporting ligands for building a range of metal complexes with different oxidation states, structures, and reactivities. This Perspective summarizes the steric and electronic influences of ligand substituents on these complexes, with an eye toward informing the design of new complexes with optimized properties. The backbone and N-aryl substituents can give significant steric effects on structure, reactivity and selectivity of reactions. The electron density on the metal can be tuned by installation of electron withdrawing or donating groups on the beta-diketiminate ligand as well. Examples are shown from throughout the transition metal series to demonstrate different types of effects attributable to systematic variation of beta-diketiminate ligands.
引用
收藏
页码:16654 / 16670
页数:17
相关论文
共 123 条
[1]   Effects of thioether substituents on the O2 reactivity of β-diketiminate-Cu(I) complexes:: Probing the role of the methionine ligand in copper monooxygenases [J].
Aboelella, NW ;
Gherman, BF ;
Hill, LMR ;
York, JT ;
Holm, N ;
Young, VG ;
Cramer, CJ ;
Tolman, WB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (10) :3445-3458
[2]   Snapshots of dioxygen activation by copper:: The structure of a 1:1 Cu/O2 adduct and its use in syntheses of asymmetric bis(μ-oxo) complexes [J].
Aboelella, NW ;
Lewis, EA ;
Reynolds, AM ;
Brennessel, WW ;
Cramer, CJ ;
Tolman, WB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (36) :10660-10661
[3]   Cu(I) β-diketiminates for alkene aziridination:: Reversible Cu-arene binding and catalytic nitrene transfer from Phl=NTs [J].
Amisial, LD ;
Dai, XL ;
Kinney, RA ;
Krishnaswamy, A ;
Warren, TH .
INORGANIC CHEMISTRY, 2004, 43 (21) :6537-6539
[4]   Palladium β-diiminate chemistry: Reactivity towards monodentate ligands and arylboronic acids [J].
Annibale, Vincent T. ;
Tan, Runyu ;
Janetzko, John ;
Lund, Liisa M. ;
Song, Datong .
INORGANICA CHIMICA ACTA, 2012, 380 :308-321
[5]   Electronic structure and electrophilic reactivity of discrete copper diphenylcarbenes [J].
Badiei, YM ;
Warren, TH .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2005, 690 (24-25) :5989-6000
[6]   Four-coordinate titanium alkylidene complexes: Synthesis, reactivity, and kinetic studies involving the terminal neopentylidene functionality [J].
Basuli, F ;
Bailey, BC ;
Watson, LA ;
Tomaszewski, J ;
Huffman, JC ;
Mindiola, DJ .
ORGANOMETALLICS, 2005, 24 (08) :1886-1906
[7]   Terminal zirconium imides prepared by reductive C-N bond cleavage [J].
Basuli, F ;
Kilgore, UJ ;
Brown, D ;
Huffman, JC ;
Mindiola, DJ .
ORGANOMETALLICS, 2004, 23 (26) :6166-6175
[8]   A terminal and four-coordinate titanium alkylidene prepared by oxidatively induced α-hydrogen abstraction [J].
Basuli, F ;
Bailey, BC ;
Tomaszewski, J ;
Huffman, JC ;
Mindiola, DJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (20) :6052-6053
[9]   Carbon-oxygen bond cleavage promoted by a scandium borohydride complex [J].
Basuli, F ;
Tomaszewski, J ;
Huffman, JC ;
Mindiola, DJ .
ORGANOMETALLICS, 2003, 22 (23) :4705-4714
[10]   Well- Defined Four- Coordinate Iron( II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines** [J].
Bernoud, Elise ;
Oulie, Pascal ;
Guillot, Regis ;
Mellah, Mohamed ;
Hannedouche, Jerome .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (19) :4930-4934