[1:3] Site-differentiated and sulfide-bridged cubane clusters in chemistry and biology

被引:17
作者
Holm, RH [1 ]
机构
[1] Harvard Univ, Dept Chem & Biol Chem, Cambridge, MA 02138 USA
基金
美国国家卫生研究院;
关键词
D O I
10.1351/pac199870040931
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A subset of protein-bound Fe4S4 cubane-type clusters occurs in a [1:3] iron site-differentiated form in which the terminal ligand at the unique site is not a cysteinyl group. Reactions of synthetic site-differentiated [Fe4S4](2+) clusters are summarized, including removal of the unique iron atom to afford the [Fe3S4](0) cuboidal cluster, thereby completing the synthesis of analogues of native iron-sulfur clusters with nuclearity 14. The cuboidal cluster supports metal ion insertion reactions leading to a set of heterometal cubane type clusters MFe3S4, whose redox potentials have been determined as a function of M. Sulfide-bridged double cubanes [MFe3S4]-S-[MFe3S4] (M = Mo, Fe; M-2 = MoFe), another type of site-differentiated cluster, have been prepared as precursors in potential cluster rearrangement reactions leading to the core [MFe6S9] with the same topology as the FeMo-cofactor of nitrogenase.
引用
收藏
页码:931 / 938
页数:8
相关论文
共 40 条
[1]  
BEINERT H, IN PRESS SCIENCE
[2]   INVESTIGATION OF METAL-ION UPTAKE REACTIVITIES OF [3FE-4S] CLUSTERS IN PROTEINS - VOLTAMMETRY OF COADSORBED FERREDOXIN AMINOCYCLITOL FILMS AT GRAPHITE-ELECTRODES AND SPECTROSCOPIC IDENTIFICATION OF TRANSFORMED CLUSTERS [J].
BUTT, JN ;
ARMSTRONG, FA ;
BRETON, J ;
GEORGE, SJ ;
THOMSON, AJ ;
HATCHIKIAN, EC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (17) :6663-6670
[3]   SYNTHESIS AND ELECTRON DELOCALIZATION OF [FE4S4]-S-FE(III) BRIDGED ASSEMBLIES RELATED TO THE EXCHANGE-COUPLED CATALYTIC SITE OF SULFITE REDUCTASES [J].
CAI, LS ;
HOLM, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (16) :7177-7188
[4]   IRON-SULFUR CLUSTERS IN ENZYMES - THEMES AND VARIATIONS [J].
CAMMACK, R .
ADVANCES IN INORGANIC CHEMISTRY, 1992, 38 :281-322
[5]   HETEROMETAL CLUSTERS CONTAINING THE CUBOIDAL FE4S3 FRAGMENT - SYNTHESIS, ELECTRON-DISTRIBUTION, AND REACTIONS [J].
CEN, W ;
MACDONNELL, FM ;
SCOTT, MJ ;
HOLM, RH .
INORGANIC CHEMISTRY, 1994, 33 (25) :5809-5818
[6]   NEW MU-2-S2--COUPLED, SINGLY BRIDGED DOUBLE CUBANE WITH THE [(FE4S4CL3)2S]4- CORE - THE STEPWISE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF (ETA-BU4N)2(PH4P)2[(FE4S4CL3)2S] [J].
CHALLEN, PR ;
KOO, SM ;
DUNHAM, WR ;
COUCOUVANIS, D .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (06) :2455-2456
[7]   THE NITROGENASE FEMO-COFACTOR AND P-CLUSTER PAIR - 2.2-ANGSTROM RESOLUTION STRUCTURES [J].
CHAN, MK ;
KIM, JS ;
REES, DC .
SCIENCE, 1993, 260 (5109) :792-794
[8]   SUBSITE-DIFFERENTIATED ANALOGS OF NATIVE [4FE-4S]2+ CLUSTERS - PREPARATION OF CLUSTERS WITH 5-COORDINATE AND 6-COORDINATE SUBSITES AND MODULATION OF REDOX POTENTIALS AND CHARGE-DISTRIBUTIONS [J].
CIURLI, S ;
CARRIE, M ;
WEIGEL, JA ;
CARNEY, MJ ;
STACK, TDP ;
PAPAEFTHYMIOU, GC ;
HOLM, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (07) :2654-2664
[9]   SULFITE REDUCTASE STRUCTURE AT 1.6 ANGSTROM - EVOLUTION AND CATALYSIS FOR REDUCTION OF INORGANIC ANIONS [J].
CRANE, BR ;
SIEGEL, LM ;
GETZOFF, ED .
SCIENCE, 1995, 270 (5233) :59-67
[10]   SYNTHESIS, STRUCTURAL CHARACTERIZATION, AND PROPERTIES OF NEW SINGLE AND DOUBLE CUBANES CONTAINING THE MOFE3S4 STRUCTURAL UNIT AND MOLYBDENUM-BOUND POLYCARBOXYLATE LIGANDS - CLUSTERS WITH A MOLYBDENUM-COORDINATION ENVIRONMENT SIMILAR TO THAT IN THE IRON MOLYBDENUM COFACTOR OF NITROGENASE [J].
DEMADIS, KD ;
COUCOUVANIS, D .
INORGANIC CHEMISTRY, 1995, 34 (02) :436-448