Double Deprotonation of CH3CN by an Iron-Aluminium Complex

被引：0

作者：

Stadler, Benedek ^{[1
]}

Gorgas, Nikolaus ^{[1
,2
]}

White, Andrew J. P. ^{[1
]}

Crimmin, Mark R. ^{[1
]}

机构：

[1] Imperial Coll London, Dept Chem, London W12 0BZ, England

[2] Vienna Univ Technol, Inst Appl Synthet Chem, Getreidemarkt 9, A-1060 Vienna, Austria

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 16期

基金：

欧洲研究理事会; 奥地利科学基金会;

关键词：

Aluminium; C-H Activation; Dianions; Iron; Nitriles; BOND ACTIVATION; C-H; ALPHA; ACETONITRILE; NITRILES; HYDROGEN; CRYSTAL; LI;

D O I：

10.1002/anie.202219212

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein we present the first double deprotonation of acetonitrile (CH3CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN](2-) dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH2CN](-) complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts.([1, 2]) The isolation of a [CHCN](2-) dianion through simple deprotonation of CH3CN also offers the possibility of establishing a broader chemistry of this motif.

引用

页数：5

共 27 条

[1] DINUCLEAR CYANOALKYLIDENE COMPLEXES OF IRON
ALBANO, VG
BORDONI, S
BRAGA, D
BUSETTO, L
PALAZZI, A
ZANOTTI, V
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1991, 30 (07) : 847 - 849
[2] [Anonymous], 1991, ANGEW CHEM, V103, P895
[3] [Anonymous], 1986, ANGEW CHEM
[4] Arseniyadis S., 1984, ORG REACTIONS, P1
[5] [(ALPHA-CYANOBENZYLLITHIUM.TETRAMETHYL-ETHYLENEDIAMINE)2.BENZENE] - X-RAY STRUCTURE-ANALYSIS OF AN ALPHA-NITRILE CARBANION
BOCHE, G
MARSCH, M
HARMS, K
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (04): : 373 - 374
[6] Structure and reactivity studies of the first tungsten cyanoalkylidene complex
Cameron, TM
Gamble, AS
Abboud, KA
Boncella, JM
[J]. CHEMICAL COMMUNICATIONS, 2002, (10) : 1148 - 1149
[7] SYNTHESIS AND REACTIONS OF ALPHA-LI-N,N-DIMETHYL-ACETAMIDE AND-PROPIONAMIDE AND ALPHA-LI-ACETONITRILE
CROUSE, DN
SEEBACH, D
[J]. CHEMISCHE BERICHTE-RECUEIL, 1968, 101 (09): : 3113 - &
[8] CH3CN: X-ray structural investigation of a unique single crystal.: β→α phase transition and crystal structure
Enjalbert, R
Galy, J
[J]. ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 2002, 58 : 1005 - 1010
[9] C-H vs C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs Nickel and Cp* vs Tp′ (Tp′ = Hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp* = η5-Pentamethylcyclopentadienyl)
Evans, Meagan E.
Li, Ting
Jones, William D.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (45) : 16278 - 16284
[10] Addition of nitriles to alkaline earth metal complexes of 1,2-bis[(phenyl)imino]acenaphthenes
Fedushkin, IL
Morozov, AG
Rassadin, OV
Fukin, GK
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (19) : 5749 - 5757

← 1 2 3 →