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
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
收藏
页码:1900 / 1907
页数:8
相关论文
共 37 条
[11]   Flexibility of liver alcohol dehydrogenase in stereoselective binding of 3-butylthiolane 1-oxides [J].
Cho, H ;
Ramaswamy, S ;
Plapp, BV .
BIOCHEMISTRY, 1997, 36 (02) :382-389
[12]   CRYSTAL-STRUCTURES OF ZN(SR)2 COMPLEXES - STRUCTURAL MODELS FOR THE PROPOSED [ZN(CYS-S)2(HIS)2] CENTER IN TRANSCRIPTION FACTOR-IIIA AND RELATED NUCLEIC-ACID BINDING-PROTEINS [J].
CORWIN, DT ;
KOCH, SA .
INORGANIC CHEMISTRY, 1988, 27 (03) :493-496
[14]  
DILWORTH JR, 1993, ADV INORG CHEM, V40, P411, DOI DOI 10.1016/S0898-8838(08)60187-7
[15]  
EKLUND, 1986, ZINC ENZYMES
[16]   ZINC-COMPLEXES OF AMINO-ACIDS AND PEPTIDES .2. COORDINATION OF SIMPLE HISTIDINE DERIVATIVES TO ZINC [J].
FORSTER, M ;
BURTH, R ;
POWELL, AK ;
EICHE, T ;
VAHRENKAMP, H .
CHEMISCHE BERICHTE-RECUEIL, 1993, 126 (12) :2643-2648
[17]   MIXED AMIDE THIOLATE COMPLEXES OF ZINC WITH LOW COORDINATION-NUMBER AT THE METAL ATOM [J].
GRUTZMACHER, H ;
STEINER, M ;
PRITZKOW, H ;
ZSOLNAI, L ;
HUTTNER, G ;
SEBALD, A .
CHEMISCHE BERICHTE-RECUEIL, 1992, 125 (10) :2199-2207
[18]   CRYSTAL-STRUCTURES OF CHLORO- AND BROMO-(2-DIETHYLAMINOETHANOLATO)-ZINC(II) [J].
HAASE, W ;
MERGEHENN, R ;
ALLMANN, R .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1975, 31 (APR15) :1184-1186
[19]   SYNTHESIS AND COORDINATING PROPERTIES OF LIGANDS DESIGNED FOR MODELING OF THE ACTIVE-SITE ZINC OF LIVER ALCOHOL-DEHYDROGENASE [J].
KAPTEIN, B ;
BARF, G ;
KELLOGG, RM ;
VANBOLHUIS, F .
JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (06) :1890-1901
[20]  
KELLER E, 1997, SCHAKAL WINDOWS