Catalytic functions of cubane-type M4S4 clusters

Seino, Hidetake; Hidai, Masanobu

doi:10.1039/c0sc00545b

Cited by 84 publications

(69 citation statements)

References 137 publications

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“…Metalloproteins containing [Fe4S4] clusters carry out a broad series of reactions 1,2 . For example, aconitase 3 catalyses the hydration of the alkene-containing species cis -aconitate to citrate and iso-citrate, whereas ferredoxins 1,4 mediate electron transfer reactions.…”

Section: Introductionmentioning

confidence: 99%

Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

Span

Wang

et al. 2012

Nat Commun

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The final step of the methylerythritol phosphate isoprenoid biosynthesis pathway is catalysed by the iron–sulphur enzyme IspH, producing the universal precursors of terpenes: isopentenyl diphosphate and dimethylallyl diphosphate. Here we report an unforeseen reaction discovered during the investigation of the interaction of IspH with acetylene inhibitors by X-ray crystallography, Mößbauer, and nuclear magnetic resonance spectroscopy. In addition to its role as a 2H+/2e− reductase, IspH can hydrate acetylenes to aldehydes and ketones via anti-Markovnikov/Markovnikov addition. The reactions only occur with the oxidised protein and proceed via η1-O-enolate intermediates. One of these is characterized crystallographically and contains a C4 ligand oxygen bound to the unique, fourth iron in the 4Fe-4S cluster: this intermediate subsequently hydrolyzes to produce an aldehyde product. This unexpected side to IspH reactivity is of interest in the context of the mechanism of action of other acetylene hydratases, as well as in the design of antiinfectives targeting IspH.

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Section: Introductionmentioning

confidence: 99%

Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

Span

Wang

et al. 2012

Nat Commun

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“…1 In this context, cuboidal M 3 S 4 (M=Mo, W) cluster chalcogenides, represented in Figure 1, and their closely related heterobimetallic M 3 M'S 4 (M'= transition metal) complexes, have been extensively investigated. 2 In general molybdenum and tungsten M 3 S 4 clusters are electron precise with six electrons for the formation of three metal-metal bonds and a formal oxidation state of +4 for the metals, Mo or W. Particular attention has been placed in our groups to their diphosphino [M 3 S 4 X 3 (diphosphine) 3 ] + (X= halide, hydride) derivatives, because of the major role that transition metal complexes containing phosphines play in homogeneous catalysis. [3][4][5][6][7][8][9][10][11] The coordination mode of the diphosphine ligands in these complexes affords a single isomer, represented in Figure 2, with one phosphorous atom trans to the capping sulfur (S c ) and one trans to the bridging sulfur (S b )…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Trinuclear W₃S₄Clusters Bearing Aminophosphine Ligands and Their Reactivity toward Halides and Pseudohalides

et al. 2014

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The aminophosphine ligand (2-aminoethyl)diphenylphosphine (edpp) has been coordinated to the W 3 (µ 3 -S)(µ-S) 3 the actual mechanism of substitutions in these clusters is strongly dependent on the nature of the leaving and entering anions. The interaction between an entering F -and the amino group coordinated to the adjacent metal have been also found to be especially relevant in the kinetics of these reactions.

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“…The catalytic potential of these cubane-type clusters has been recently reviewed. 4 Unlike numerous examples of molybdenum and tungsten M 3 Q 4 clusters, their Re analogues remain much less investigated. 5 In 1990 the first synthesis of a family of Re(V) trinuclear cluster chalcogenides of formula [Re 3 Q 7 X 6 ]X (Q = S, Se; X = Cl, Br) was reported.…”

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Synthesis, molecular and electronic structure of an incomplete cuboidal Re3S4 cluster with an unusual quadruplet ground state

et al. 2012

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A Re(IV) cluster complex [Re 3 (l 3 -S)(l-S) 3 (dppe) 3 Br 3 ] + with nine cluster skeletal electrons (CSE) and a quadruplet ground state has been prepared by treatment of [Re 3 S 7 Br 6 ]Br with 1,2-bis(diphenylphosphino)ethane (dppe) in MeCN.Triangular clusters with incomplete cuboidal M 3 (m 3 -Q)(m-Q) 3 cores (Q = S, Se) are basic units in the chemistry of the heaviest group six transition metal cluster chalcogenides.1 With a single reported exception, 2 M 3 Q 4 (M = Mo, W) clusters are electron precise with six CSE for the formation of three metalmetal bonds that results in stable diamagnetic complexes.3 These M 3 Q 4 compounds are building blocks for the formation of heterobimetallic M 3 Q 4 M 0 species with variable CSE populations ranging from 13 to 17 electrons. The catalytic potential of these cubane-type clusters has been recently reviewed. 4 Unlike numerous examples of molybdenum and tungsten M 3 Q 4 clusters, their Re analogues remain much less investigated. 5 In 1990 the first synthesis of a family of Re(V) trinuclear cluster chalcogenides of formula [Re 3 Q 7 X 6 ]X (Q = S, Se; X = Cl, Br) was reported.6 In these systems with six CSE and three metalmetal bonds, the rhenium atoms define an equilateral triangle with a capping chalcogen and three bridging dichalcogenides. The cluster core in [Re 3 Q 7 X 6 ]X shares structural and electronic features with the M 3 (m 3 -Q)(m-Q 2 ) 3 unit found in the polymeric {M 3 Q 7 X 4/2 X 2 } N (M = Mo, W) phases, widely used as starting materials for the preparation of molybdenum and tungsten M 3 Q 4 cuboidal complexes upon treatment with phosphanes. (Fig. 1) was established by single crystal X-ray diffraction experimentsy and it shares structural features with its molybdenum and tungsten analogues. The metal atoms in Re 3 S 4 define an almost equilateral triangle (average Re-Re distance 2.780[9] Å ) with one capping m 3 -S atom and three bridging m-S. The Re 3 S 4 unit can also be regarded as an incomplete cube in which the metal and sulfur atoms occupy adjacent vertex with a missing rhenium atom. The Re-(m-S) distances that are roughly trans to a Re-P bond are noticeably (by 0.05 Å ) longer than those trans to the Re-Br bond. The two types of Re-P distances also differ, the one trans to m 3 -S ligand being ca. 0.03 Å shorter (see Table 1).

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Catalytic functions of cubane-type M4S4 clusters

Cited by 84 publications

References 137 publications

Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

Synthesis and Structure of Trinuclear W₃S₄Clusters Bearing Aminophosphine Ligands and Their Reactivity toward Halides and Pseudohalides

Synthesis, molecular and electronic structure of an incomplete cuboidal Re3S4 cluster with an unusual quadruplet ground state

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Catalytic functions of cubane-type M4S4 clusters

Cited by 84 publications

References 137 publications

Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

Discovery of acetylene hydratase activity of the iron–sulphur protein IspH

Synthesis and Structure of Trinuclear W3S4Clusters Bearing Aminophosphine Ligands and Their Reactivity toward Halides and Pseudohalides

Synthesis, molecular and electronic structure of an incomplete cuboidal Re3S4 cluster with an unusual quadruplet ground state

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Synthesis and Structure of Trinuclear W₃S₄Clusters Bearing Aminophosphine Ligands and Their Reactivity toward Halides and Pseudohalides