Structure and properties of [Fe4S4{2,6-bis(acylamino)benzenethiolato-S}(4)](2-) and [Fe2S2{2,6-bis(acylamino)benzenethiolato-S}(4)](2-): Protection of the Fe-S bond by double NH center dot center dot center dot S hydrogen bonds

被引:76
作者
Ueyama, N
Yamada, Y
Okamura, T
Kimura, S
Nakamura, A
机构
[1] Department of Macromolecular Science, Faculty of Science, Osaka University, Toyonaka
关键词
D O I
10.1021/ic9604324
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Iron-sulfur clusters containing a singly or doubly NH...S hydrogen-bonded arenethiolate ligand, [Fe4S4(S-2-RCONHC(6)H(4))(4)](2-) (R = CH3, t-Bu, CF3), [Fe4S4{S-2,6-(RCONH)(2)C6H3}(4)](2-), [Fe2S2(S-2-RCONHC(6)H(4))(4)](2-) (R = CH3, t-Bu, CF3), and [Fe2S2{S-2,6-(RCONH)(2)C6H3}(4)](2-), were synthesized as models of bacterial [4Fe-4S] and plant-type [2Fe-2S] fenedoxins. The X-ray structures and IR spectra of (PPh(4))(2)[Fe4S4{S-2,6-(CH3-CONH)(2)C6H3}(4)]. 2CH(3)CN and (NEt(4))(2)[Fe2S2{S-2,6-(t-BuCONH)(2)C6H3}(4)] indicate that the two amide NH groups at the o,o'-positions are directed to the thiolate sulfur atom and form double NH...S hydrogen bonds. The NH...S hydrogen bond contributes to the positive shift of the redox potential of not only (Fe4S4)(+)/(Fe4S4)(2+) but also (Fe4S4)(2+)/(Fe4S4)(3+) in the [4Fe-4S] clusters as well as (Fe2S2)(2+)/(Fe2S2)(3+) in the [2Fe-2S] clusters. The doubly NH...S hydrogen-bonded thiolate ligand effectively prevents the ligand exchange reaction by benzenethiol because the two amide NH groups stabilize the thiolate by protection from dissociation.
引用
收藏
页码:6473 / 6484
页数:12
相关论文
共 67 条
[21]   ROLE OF THE CENTRAL THIOL IN DETERMINING RATES OF THE THIOL-DISULFIDE INTERCHANGE REACTION [J].
FRETER, R ;
POHL, ER ;
WILSON, JM ;
HUPE, DJ .
JOURNAL OF ORGANIC CHEMISTRY, 1979, 44 (11) :1771-1774
[22]   TERTIARY STRUCTURE OF BACILLUS-THERMOPROTEOLYTICUS [4FE-4S] FERREDOXIN - EVOLUTIONARY IMPLICATIONS FOR BACTERIAL FERREDOXINS [J].
FUKUYAMA, K ;
NAGAHARA, Y ;
TSUKIHARA, T ;
KATSUBE, Y ;
HASE, T ;
MATSUBARA, H .
JOURNAL OF MOLECULAR BIOLOGY, 1988, 199 (01) :183-193
[23]   STRUCTURE OF S-PLATENSIS [2FE-2S] FERREDOXIN AND EVOLUTION OF CHLOROPLAST-TYPE FERREDOXINS [J].
FUKUYAMA, K ;
HASE, T ;
MATSUMOTO, S ;
TSUKIHARA, T ;
KATSUBE, Y ;
TANAKA, N ;
KAKUDO, M ;
WADA, K ;
MATSUBARA, H .
NATURE, 1980, 286 (5772) :522-524
[24]   QUANTITATIVE EXTRUSIONS OF FE4S4-STAR CORES OF ACTIVE-SITES OF FERREDOXINS AND HYDROGENASE OF CLOSTRIDIUM-PASTEURIANUM [J].
GILLUM, WO ;
MORTENSON, LE ;
CHEN, JS ;
HOLM, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (02) :584-595
[25]   DEFINITION OF REACTION SEQUENCES RESULTING IN SELF-ASSEMBLY OF [FE4S4(SR)4]2- CLUSTERS FROM SIMPLE REACTANTS [J].
HAGEN, KS ;
REYNOLDS, JG ;
HOLM, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (14) :4054-4063
[26]   SYNTHETIC ANALOGS OF ACTIVE-SITES OF IRON-SULFUR PROTEINS .15. COMPARATIVE POLAROGRAPHIC POTENTIALS OF [FE4S4(SR)4]2-,3- AND CLOSTRIDIUM-PASTEURIANUM FERREDOXIN REDOX COUPLES [J].
HILL, CL ;
RENAUD, J ;
HOLM, RH ;
MORTENSON, LE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (08) :2549-2557
[27]   SYNTHETIC APPROACHES TO ACTIVE-SITES OF IRON-SULFUR PROTEINS [J].
HOLM, RH .
ACCOUNTS OF CHEMICAL RESEARCH, 1977, 10 (12) :427-434
[28]   SYNTHETIC ANALOGS OF ACTIVE-SITES OF IRON-SULFUR PROTEINS .5. PROTON-RESONANCE PROPERTIES OF TETRANUCLEAR CLUSTERS [FE4S4(SR)4]2- - EVIDENCE FOR DOMINANT CONTACT INTERACTIONS [J].
HOLM, RH ;
PHILLIPS, WD ;
AVERILL, BA ;
MAYERLE, JJ ;
HERSKOVITZ, T .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (07) :2109-2117
[29]   HYDROGEN-BONDING AND POLAR GROUP EFFECTS ON REDOX POTENTIALS IN MO[HB(ME(2)PZ)(3)] (NO)(SR)(2) [J].
HUANG, J ;
OSTRANDER, RL ;
RHEINGOLD, AL ;
LEUNG, YC ;
WALTERS, MA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (15) :6769-6776
[30]   A REEXAMINATION OF THE HAMMETT EQUATION [J].
JAFFE, HH .
CHEMICAL REVIEWS, 1953, 53 (02) :191-261