Homoleptic group 12 metal bis(mercaptoimidazolyl)borate complexes M(BMR)2 (M = Zn, Cd, Hg)

被引:64
作者
Alvarez, HM
Tran, TB
Richter, MA
Alyounes, DM
Rabinovich, D
Tanski, JM
Krawiec, M
机构
[1] Univ N Carolina, Dept Chem, Charlotte, NC 28223 USA
[2] Columbia Univ, Dept Chem, New York, NY 10027 USA
[3] Clemson Univ, Dept Chem, Ctr Mol Struct, Clemson, SC 29634 USA
关键词
D O I
10.1021/ic025780m
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The sodium salt of the bis(2-mercapto-1-methylimidazolyl)borate anion [Bm(Me)](-) and those of the new bis(2-mercapto-1-alkylimidazolyl)borates [BMR](-) (R = Bz, Bu-t, p-Tol) have been readily obtained from NaBH4 and the appropriate 2-mercapto-1-alkylimidazoles. To contrast the binding preferences of the group 12 metals in a sulfur-rich environment, the four complete series of homoleptic complexes M[Bm(R)](2) (M = Zn, Cd, Hg), including the first bis(mercaptoimidazolyl)borate derivatives of cadmium and mercury, have been prepared. X-ray diffraction studies of Cd[Bm(Me)](2) and M[Bm(tBu)](2) (M = Zn, Cd, Hg) show the presence of distorted tetrahedral [MS4] central cores supplemented by two weak vicinal M...H-B bonds, interactions which appear to be a common feature in the coordination chemistry of Bm(R) ligands. In the case of zinc, it has been found that only in the presence of bulky ligands, as in Zn[Bm(tBu)](2), may an unexpected expansion in the coordination number from four to six be induced. This observation suggests the viability of octahedral intermediates in the processes whereby certain zinc enzymes transfer or exchange metal ions.
引用
收藏
页码:2149 / 2156
页数:8
相关论文
共 41 条
[1]  
Allen F.H., 1993, CHEM AUTOMAT NEWS, V8, P31
[2]   Modeling nickel hydrogenases:: Synthesis and structure of a distorted octahedral complex with an unprecedented [NiS4H2] core [J].
Alvarez, HM ;
Krawiec, M ;
Donovan-Merkert, BT ;
Fouzi, M ;
Rabinovich, D .
INORGANIC CHEMISTRY, 2001, 40 (23) :5736-+
[3]  
ALVAREZ HM, 1997, UNPUB
[4]   Synthesis and characterization of novel mononuclear cadmium thiolate complexes in a sulfur-rich environment [J].
Bakbak, S ;
Incarvito, CD ;
Rheingold, AL ;
Rabinovich, D .
INORGANIC CHEMISTRY, 2002, 41 (04) :998-+
[5]   Synthesis and characterization of two new bulky tris(mercaptoimidazolyl)borate ligands and their zinc and cadmium complexes [J].
Bakbak, S ;
Bhatia, VK ;
Incarvito, CD ;
Rheingold, AL ;
Rabinovich, D .
POLYHEDRON, 2001, 20 (28) :3343-3348
[6]   Three-center, two-electron M•••H-B bonds in complexes of Ni, Co, and Fe and the dihydrobis(3-tert-butylpyrazolyl) borate ligand [J].
Belderraín, TR ;
Paneque, M ;
Carmona, E ;
Gutiérrez-Puebla, E ;
Monge, MA ;
Ruiz-Valero, C .
INORGANIC CHEMISTRY, 2002, 41 (02) :425-+
[7]   Complexes of heterocyclic thiones and Group 12 metals -: Part 3.: Preparation and characterisation of 1:2 complexes of mercury(II) halides with 1-methylimidazoline-2(3H)-thione:: the crystal structures of [(HgX2)(1-methylimidazoline-2(3H)-thione)2] (X = Cl, Br, I) at 160 K [J].
Bell, NA ;
Branston, TN ;
Clegg, W ;
Creighton, JR ;
Cucurull-Sánchez, L ;
Elsegood, MRJ ;
Raper, ES .
INORGANICA CHIMICA ACTA, 2000, 303 (02) :220-227
[8]   A zinc thiolate species which mimics aspects of the chemistry of the Ada repair protein and matrix metalloproteinases:: the synthesis, structure and reactivity of the tris(2-mercapto-1-phenylimidazolyl)hydroborato complex [TmPh]ZnSPh [J].
Bridgewater, BM ;
Fillebeen, T ;
Friesner, RA ;
Parkin, G .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (24) :4494-4496
[9]   Lead poisoning and the inactivation of 5-aminolevulinate dehydratase as modeled by the tris(2-mercapto-1-phenylimidazolyl)hydroborato lead complex, {[TmPh]Pb}[ClO4] [J].
Bridgewater, BM ;
Parkin, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (29) :7140-7141
[10]   The synthesis and molecular structure of [TmPh]2Pb:: a complex with an 'inverted' η4-coordination mode for the tris(2-mercapto-1-phenylimidazolyl)hydroborato ligand [J].
Bridgewater, BM ;
Parkin, G .
INORGANIC CHEMISTRY COMMUNICATIONS, 2000, 3 (10) :534-536