Author
Peter V. Broadhurst
Other affiliations: University of Cambridge
Bio: Peter V. Broadhurst is an academic researcher from Union Carbide. The author has contributed to research in topics: Ligand & Crystal structure. The author has an hindex of 6, co-authored 11 publications receiving 170 citations. Previous affiliations of Peter V. Broadhurst include University of Cambridge.
Papers
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TL;DR: A systematic literature review is provided of CS ligand-preparative methods used to form thiocarbonyl complexes between 1812 and 1814, and their applications in Fe triad, Mntriad, and Cotriad.
90 citations
TL;DR: In this article, a single-crystal X-ray analysis was carried out on Dodecacarbonyltri-iron [Fe3(CO)12] for hexane under a CO-Ar atmosphere (1:1, pressure ca. 10 atm).
Abstract: Dodecacarbonyltri-iron, [Fe3(CO)12], reacts with an execess of CS2 in hexane at 80 °C under a CO–Ar atmosphere (1:1, pressure ca. 10 atm) to give a number of products in including, in low yield, [Fe4(CO)12(C2S4)] which, on the basis of a single-crystal X-ray analysis, has been shown to contain two Fe2(CO)6 units bridged by a C2S4 unit which may be regarded as a derivative of ethenetetrathiol.
20 citations
15 citations
TL;DR: In this article, the properties of the three possible isomers of these compounds are characterized on the basis of their spectroscopic properties and only one of these isomeric forms is produced.
Abstract: The cluster [Os3(CO)11(NCMe)] reacts with the compounds R2E2(E = S, R = Me, Ph, or CH2Ph; E = Se, R = Ph) to give the clusters [Os3(CO)10(µ-ER)2] which have been fully characterised on the basis of their spectroscopic properties. In each case, only one of the three possible isomers of these compounds is produced. On heating, [Os3(CO)10(µ-SMe)2] converts to a second isomeric form which is isostructural with the known compound [Os3(CO)10(µ-OMe)2], whereas the compounds [Os3(CO)10(µ-ER)2](E = S, R = Ph or CH2Ph; E = Se, R = Ph) give small yields of [Os3(CO)9E2](E = S or Se) and [Os3(CO)9(SR)2](E = S or Se, R = Ph).
12 citations
TL;DR: In this article, the reaction of CS2 with H2Os3(CO)8(MeCN)S in cyclohexane yields a product H2O3CO)7(CS)S2, which has been characterised by NMR and mass spectroscopy, and by X-ray analysis.
9 citations
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TL;DR: This article sets out to review the chemistry relating to the synthesis of structural and functional analogues of the three classes of hydrogenases, including the di-iron system.
Abstract: This article sets out to review the chemistry relating to the synthesis of structural and functional analogues of the three classes of hydrogenases. This chemistry has grown explosively over the last 10 or so years since the first X-ray structures of [NiFe]- and [FeFe]-hydrogenase systems were published. There are now some 400 papers covering structural and functional aspects, with the majority of these associated with the di-iron system. As much emphasized in earlier papers
1,135 citations
TL;DR: These reactions are reviewed in light of major advances over the past few decades, spurred by interest in Fe2(μ-SR)2(CO)x centers at the active sites of the [FeFe]-hydrogenase enzymes.
Abstract: Virtually all organosulfur compounds react with Fe(0) carbonyls to give the title complexes. These reactions are reviewed in light of major advances over the past few decades, spurred by interest in Fe2(μ-SR)2(CO)x centers at the active sites of the [FeFe]-hydrogenase enzymes. The most useful synthetic route to Fe2(μ-SR)2(CO)6 involves the reaction of thiols with Fe2(CO)9 and Fe3(CO)12. Such reactions can proceed via mono-, di-, and triiron intermediates. The reactivity of Fe(0) carbonyls toward thiols is highly chemoselective, and the resulting dithiolato complexes are fairly rugged. Thus, many complexes tolerate further synthetic elaboration directed at the organic substituents. A second major route involves alkylation of Fe2(μ-S2)(CO)6, Fe2(μ-SH)2(CO)6, and Li2Fe2(μ-S)2(CO)6. This approach is especially useful for azadithiolates Fe2[(μ-SCH2)2NR](CO)6. Elaborate complexes arise via addition of the FeSH group to electrophilic alkenes, alkynes, and carbonyls. Although the first example of Fe2(μ-SR)2(CO)6 ...
253 citations
TL;DR: In this article, the reduction of carbon dioxide catalyzed by transition metal complexes, using different methods, is discussed, and it is shown that removing sulfur from the metal-(η2-COS) complexes is more facile.
204 citations
152 citations
TL;DR: In this article, the authors discuss basic metal cluster reactions, such as the addition or removal of electrons, the simplest type of chemical reaction, for transition metal compounds, and the 18-electron rule generally governs the bonding in clusters with up to five metal atoms.
Abstract: Publisher Summary This chapter discusses basic metal cluster reactions Addition or removal of electrons, the simplest type of chemical reaction, is much more common for transition metal than for main group element compounds Among the metal complexes, the clusters are predestined for this process Possible unidentate reagents are atomic cations and other simple electrophiles as well as atomic anions and other simple nucleophiles All cluster syntheses involve growth or fragmentation of metal atom aggregates But until very recently, the buildup of clusters or the use of clusters as fragment sources involved empirical approaches with little predictability The 18-electron rule generally governs the bonding in clusters with up to five metal atoms Clusters with five, six, and sometimes seven metal atoms can often be treated in terms of skeletal electron counting, describing the frameworks by the nido, closo, and capping formalisms A systematization of basic cluster reactions has been attempted based on the present status of knowledge The number of reactions reported is still relatively small for certain reaction types
127 citations