The solution stability of copper(I) and silver(I) complexes with N-heterocyclic carbenes

被引:13
作者
Amendola, Valeria [1 ]
Bergamaschi, Greta [1 ]
Boiocchi, Massimo [2 ]
Fabbrizzi, Luigi [1 ]
Fusco, Nadia [1 ]
机构
[1] Univ Pavia, Dipartimento Chim Gen, I-27100 Pavia, Italy
[2] Univ Pavia, Ctr Grandi Strumenti, I-27100 Pavia, Italy
关键词
LIGANDS; EQUILIBRIUM; NHC; AU; AG;
D O I
10.1039/c1dt10894h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The tris-benzimidazolium cage LH33+, in MeCN solution, in the presence of OH-, forms with Cu-I and Ag-I ions complexes of formula [M-I(LH)](2+), in which each metal is linearly coordinated by two carbenes and one imidazolium N-H fragment remains intact. To achieve two-coordination, the two N-heterocyclic moieties of the cage make a saloon-door type motion, with a conformationally costless rotation of ca. 30 degrees each. The two [MI(LH)](2+) complexes show high thermodynamic stability and are inert with respect to metal substitution, due to the mechanical constraints imposed by the ligating framework. Complexation with Cu-I and Ag-I with the reference unidentate carbene ligand Q, derived from the benzimidazolium precursor QH(+), was studied for comparison. Both metals in MeCN form 1:1 and 1:2 complexes with the carbene ligand Q according to two stepwise equilibria. Q complexes of both metals are labile with respect to metal substitution and those of AgI are more stable than those of CuI. A significant cooperative effect has been observed with the formation of the [Ag(I)Q(2)](+) complex.
引用
收藏
页码:8367 / 8376
页数:10
相关论文
共 39 条
[1]   Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species [J].
Alderighi, L ;
Gans, P ;
Ienco, A ;
Peters, D ;
Sabatini, A ;
Vacca, A .
COORDINATION CHEMISTRY REVIEWS, 1999, 184 :311-318
[2]   The Cambridge Structural Database: a quarter of a million crystal structures and rising [J].
Allen, FH .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 2002, 58 (3 PART 1) :380-388
[3]   A STABLE CRYSTALLINE CARBENE [J].
ARDUENGO, AJ ;
HARLOW, RL ;
KLINE, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (01) :361-363
[4]   HOMOLEPTIC CARBENE SILVER(I) AND CARBENE COPPER(I) COMPLEXES [J].
ARDUENGO, AJ ;
DIAS, HVR ;
CALABRESE, JC ;
DAVIDSON, F .
ORGANOMETALLICS, 1993, 12 (09) :3405-3409
[5]  
Arduengo AJ, 1999, HELV CHIM ACTA, V82, P2348, DOI 10.1002/(SICI)1522-2675(19991215)82:12<2348::AID-HLCA2348>3.0.CO
[6]  
2-M
[7]   Imidazolium-linked cyclophanes [J].
Baker, MV ;
Bosnich, MJ ;
Williams, CC ;
Skelton, BW ;
White, AH .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1999, 52 (09) :823-825
[8]   N-heterocyclic carbene, silylene, and germylene complexes of MCl (M = Cu, Ag, Au). A theoretical study [J].
Boehme, C ;
Frenking, G .
ORGANOMETALLICS, 1998, 17 (26) :5801-5809
[9]   Simple and versatile synthesis of copper and silver N-heterocyclic carbene complexes in water or organic solvents [J].
Citadelle, Cecilia A. ;
Le Nouy, Erwan ;
Bisaro, Fabrice ;
Slawin, Alexandra M. Z. ;
Cazin, Catherine S. J. .
DALTON TRANSACTIONS, 2010, 39 (19) :4489-4491
[10]   Coinage metal catalyzed C-H bond functionalization of hydrocarbons [J].
Diaz-Requejo, M. Mar ;
Perez, Pedro J. .
CHEMICAL REVIEWS, 2008, 108 (08) :3379-3394