Alcohol and aldehyde adducts of zinc thiolates:: Structural modeling of alcoholdehydrogenase

被引：67

作者：

Müller, B ^{[1
]}

Schneider, A ^{[1
]}

Tesmer, M ^{[1
]}

Vahrenkamp, H ^{[1
]}

机构：

[1] Univ Freiburg, Inst Anorgan & Analyt Chem, D-79104 Freiburg, Germany

来源：

INORGANIC CHEMISTRY | 1999年 / 38卷 / 08期

关键词：

D O I：

10.1021/ic981227m

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Bis(pentafluorothiophenolato)zinc (1) and bis(2,4,6-triisopropylthiophenolato)zinc (2) can be combined with nitrogen-containing derivatives of benzyl alcohol and benzaldehyde to form (N,O-chelate) zinc thiolates. 2-Pyridylmethanol as well as 2-quinolylmethanol (HetMeOH) yield [(HetMeO)Zn(SR)](4) (3, 4) having a cyclo-Zn-4(mu-O)(4) backbone and only terminal SR. Likewise, thiolate 1 and 2-(dimethylamino)benzyl alcohol form zwitterionic [(dimethylammoniobenzylato)Zn(SR)(2)](2) (5) with bridging alkoxide and terminal thiolate. In contrast, 6-picolylmethanol (PicMeOH) and thiolate 1 result in [(PicMeOH)Zn(SC6F5)(2)] (6) containing zinc in a tetrahedral ZnNS2O, environment. Simple aromatic aldehydes form polymeric complexes [(RCHO)Zn(SC6F5)(2)] (7: R = p-tolyl, 8: R = mesityl) with a [Zn-S](infinity) backbone. Chelating aldehydes (CA) yield mononuclear complexes with tetrahedral ZnNS2O coordination [(CA)Zn(SC6F5)(2)] (9, CA = pyridine-2-carbaldehyde; 10, CA = 6-methylpyridine-2-carbaldehyde: 11. CA = 6-methoxypyridine-2-carbaldehyde; 12, CA = quinoline-2-carbaldehyde; 13, CA = 2-(dimethylamino)benzaldehyde). In contrast, N-methylimidaznle-2-carbaldehyde (ImA) is coordinated twice in tetrahedral [(ImA)(2)Zn(SC6F5)(2)] (14) lacking any Zn-O interactions, Pyridine-2,6-dicarbaldehyde (PDA) forms trigonal bipyramidal [(PDA)Zn(SC6F5)(2)] (15) with ZnNO2S2 ligation, The structures of 3. 4, 6, 8, 10, 11, 13, and 14 were determined crystallographically, and the structures of 5 and 15 were deduced from those of the corresponding ZnBr2 complexes. The ZnNS2O coordination pattern observed for the enzyme has been reproduced to a very good approximation. In complexes 6 and 10, which are almost superimposable, it is realized for both the corresponding alcohol and aldehyde.

引用

页码：1900 / 1907

页数：8

共 37 条

[1] X-RAY STRUCTURES OF [ZN(S2CNME2)3]- AND [ZN(C7H4NS2)3(OH2)]-, POSSIBLE INTERMEDIATES IN ZINC-ASSISTED RUBBER VULCANIZATION [J].

ASHWORTH, CC ;

BAILEY, NA ;

JOHNSON, M ;

MCCLEVERTY, JA ;

MORRISON, N ;

TABBINER, B .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1976, (18) :743-744

[2] STERICALLY HINDERED CHALCOGENOLATO COMPLEXES - MONO-MERIC AND DI-MERIC THIOLATES AND SELENOLATES OF ZINC AND CADMIUM - STRUCTURE OF ((CD(SEC6H2BUT3-2,4,6)2)2), THE 1ST 3-CO-ORDINATE CADMIUM SELENIUM COMPLEX [J].

BOCHMANN, M ;

WEBB, KJ ;

HURSTHOUSE, MB ;

MAZID, M .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (09) :2317-2323

[3] SYNTHESIS OF LOW-COORDINATE CHALCOGENOLATO COMPLEXES OF ZINC WITH O, N, S, AND P DONOR LIGANDS - MOLECULAR AND CRYSTAL-STRUCTURES OF ZN(S-T-BU3C6H2-2,4,6)2(L) (L=NC5H3ME2-2,6,PMEPH2), ZN(SE-T-BU3C6H2-2,4,6)2(OSC4H8), AND ZN(S-T-BU3C6H2-2,4,6)2(N-METHYLIMIDAZOLE)2 [J].

BOCHMANN, M ;

BWEMBYA, GC ;

GRINTER, R ;

POWELL, AK ;

WEBB, KJ ;

HURSTHOUSE, MB ;

MALIK, KMA ;

MAZID, MA .

INORGANIC CHEMISTRY, 1994, 33 (10) :2290-2296

[4] THE 1ST STABLE ALDEHYDE AND KETONE COMPLEXES OF ZINC - THE STRUCTURE OF [ZN(SEC6H2BUT3)2(PARA-O=CHC6H4OME)]2 [J].

BOCHMANN, M ;

WEBB, KJ ;

HURSTHOUSE, MB ;

MAZID, M .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (24) :1735-1737

[5] Zinc complexes of the chelating N,S,S ligand N-(2-mercaptoethyl)-2-mercaptoaniline [J].

Brand, U ;

Vahrenkamp, H .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1996, 622 (02) :213-218

[6] A NEW TRIDENTATE N,N,S LIGAND AND ITS ZINC-COMPLEXES [J].

BRAND, U ;

VAHRENKAMP, H .

INORGANIC CHEMISTRY, 1995, 34 (12) :3285-3293

[7] Design of trigonal-bipyramidal ZnN3S2 complexes [J].

Brand, U ;

Burth, R ;

Vahrenkamp, H .

INORGANIC CHEMISTRY, 1996, 35 (04) :1083-1086

[8] STRUCTURE OF LIVER ALCOHOL-DEHYDROGENASE AT 2.9-A RESOLUTION [J].

BRANDEN, CI ;

EKLUND, H ;

NORDSTROM, B ;

BOIWE, T ;

SODERLUND, G ;

ZEPPEZAUER, E ;

OHLSSON, I ;

AKESON, A .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1973, 70 (08) :2439-2442

[9] Controlled formation of tri- and octanuclear benzylthiolate complexes of zinc [J].

Burth, R ;

Gelinsky, M ;

Vahrenkamp, H .

INORGANIC CHEMISTRY, 1998, 37 (11) :2833-2836

[10] MONONUCLEAR AND DINUCLEAR ZINC(II) COMPLEXES OF BIOLOGICAL RELEVANCE - CRYSTAL-STRUCTURES OF [L2ZN](PF6)2, [L'ZN(O2CPH)2(H2O)], [L'2ZN2(MU-OH)2](CLO4)2, AND [L'2ZN2(MU-OH)(MU-CH3CO2)2](CLO4)BULLET-H2O (L = 1,4,7-TRIAZACYCLONONANE, L' = 1,4,7-TRIMETHYL-1,4,7-TRIAZACYCLONONANE) [J].

CHAUDHURI, P ;

STOCKHEIM, C ;

WIEGHARDT, K ;

DECK, W ;

GREGORZIK, R ;

VAHRENKAMP, H ;

NUBER, B ;

WEISS, J .

INORGANIC CHEMISTRY, 1992, 31 (08) :1451-1457

← 1 2 3 4 →