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Showing 1 to 20 of 22 for “"dithiolate"”.
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Ultrafast extreme ultraviolet spectroscopy of transition metal dithiolate coordination complexes
… the metal center in a series of transition metal dithiolate complexes. The behavior of these molecules after absorption of light has implications for the development of catalysts and photosensitizers using earth-abundant transition metals. The cobalt dithiolene complex, [Co(bdt)2]- (bdt = …
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1,2–Dithiolate Complexes of the Lanthanides and Actinides and High– Pressure Studies of f–Element Complexes
… americium, curium, and californium with the 1,2–dithiolate ligand maleonitrile dithiolate (mnt), which is a soft sulfur–donor ligand, contrasting with the hard oxygen–donor mellitate ligand from chapter 3. Spectroscopic, crystallographic, and high–pressure characterizations reveal increases in …
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Synthesis, characterization, and reactivity of high and low valent group 10 metal complexes supported by pyridine dithiolate ligands
Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-08-01
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Modeling The Active Site Of [NiFe]-Hydrogenase
… compounds. Attempts to isolate similar [(CO)3Fe(dithiolate)Ni(diphosphine)] complexes by reaction of the mononuclear NiII(diphosphine)(dithiolate) with Fe2(CO)9 were unsuccessful with this original route, except for [(CO)3Fe(pdt)Ni(dppe)]. The reaction of FeI2(CO)4 followed by reduction with …
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Electronic structure and transport in molecular and nanoscale electronics
… are investigated including atomic wires, benzene dithiolate, phenalenyl dithiolate and carbon nanotube with and without different types of defects.
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Synthesis of redox-active ligands and their use in hydrogenase modeling
… Chapter 4 describes the synthesis of Fe(dithiolate)(diphosphine)(CO)2 complexes as building blocks to yield bimetallic model systems. When models are constructed with non-rigid disphosphine ligands, the synthesis and isolation of FeFe systems proves challenging. However, the …
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Hydrogen production from model complexes of the [FeFe]- and [NiFe]-hydrogenase active sites
… 1999. In fact, the structurally similar diiron dithiolate hexacarbonyls had been investigated since the 1920s and had well established chemistry. However, unique compared to all other diiron dithiolates, the active-site structure of [FeFe]-hydrogenase features a rotated diiron dithiolate core, …
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The characterization and chemistry of {\it mono\/}- and {\it bis\/}-cyclopentadienyl titanium thiolates.
… affording relatively insoluble titanocene dithiolate derivatives 2.1 and 2.2 respectively. Alternatively, 2.2 can be prepared by the reaction of Cp$\rm\sb2TiPh\sb2$ with dithiol. The spectroscopic and analytical data are consistent with the formulation of 2.1 and 2.2 as the bimetallic …
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Mixed-valence bimetallic dithiolates of iron, cobalt, and nickel and their relevance to the hydrogenases
… and examination of mixed-valent bimetallic dithiolate complexes. Chapter 2 focuses on the NiRu dithiolate compound (dppe)Ni(pdt)Ru(pcymene)(dppe = 1,2-bis(diphenylphosphino)ethane; pdt = 1,3-propanedithiolate, p-cymene =p-isopropyltoluene). The protonation and oxidation chemistry of this …
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Synthesis and Reactivity of Some Organometallic Chalcogenide Complexes
Examples of Sila-1,1-dithiolate complexes, Cp$\sb2$MS$\sb2$SiMe$\sb2$ (M = Ti (8) and V) and PtS$\sb2$SiMe$\sb2$(P(C$\sb6$H$\sb5$)$\sb3$)$\sb2$, were prepared by treating (Me$\sb2$SiS)$\sb3$/Li$\sb2$S with the metal dichlorides. Compound 8 is particularly interesting because it contains two …
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Small molecule mimics of hydrogenase enzymes: synthesis, protonation, and electrocatalysis
… the active site of [FeFe]-H2ases are the amino-dithiolate cofactor that bridges the two Fe centers and the rotated geometry of one Fe center, leaving an open coordination site adjacent to the amine, which is the proposed site of substrate binding. Many active site models have been prepared, many …
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The synthesis of novel organometallic materials.
… derivatives incorporate two thioether and two dithiolate environments as the overall chelating entity. The thioether functionalities are linked via suitable spacer groups and this feature should present a major advantage over traditional DMIT complexes, by adding solubility and synthetic …
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A combined approach of electronic structure calculations and spectroscopy for elucidating reaction mechanisms in organic and bioinorganic systems
… across the Fe centres are compared for di�erent dithiolate bridge groups and PMe3 ligand positions. In the pursuit of understanding the protonation mechanism of [FeFe]-hydrogenases, transition state theory is used and the energetics of reaction pathways leading to terminal and bridging hydrides …
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Applications for the activation of hydroxyl groups to nucleophilic attack
… with 2-thioxo-1,3-dithiole-4,5-dithiolate and several further steps. A triiodide complex of a tetrahydroxy substituted donor was prepared and structurally characterized.
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Studies of immobilized homogeneous metal catalysts on silica supports
… benzene, or cyclohexane.;The oxorhenium(V) dithiolate catalyst [-S(CH2)3S-]Re(O)(Me)(PPh 3) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and …
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Eta5-pentamethylcyclopentadienyl ruthenium complexes containing sulfur ligands
… (2.15) with the sodium salt of ethane-1,2-dithiolate. Complex 2.15 was reacted with groups 10 and 11 metal fragments Ni(PPh3)2Cl2, Pt(PPh3)2Cl2 and Au(PPh3)Cl to yield {Cp*Ru(S2CNMe2)(SCH2CH2S)]2Ni}(PF6)2 (2.16), [Cp*Ru(S2CNMe2)(S(CH2)2S) Pt(PPh3)2](PF6)2 (2.17) and …
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Understanding the [Fe Fe]-Hydrogenase H-Cluster: Insights From Chemical Modelling and Advanced Spectroscopy
… bulky substituents are incorporated into the dithiolate bridgehead. A comprehensive examination of their structural features and spectroscopic properties is provided. Chapter 3 reports extensive stopped-flow UV-vis, IR and electrochemical studies for a range of subsite models exploring the …
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Photophysical studies of silver(I), platinum(II), palladium(II), and nickel(II) complexes and their use in electronic devices.
… (M= Pt(II), Pd(II), or Ni(II); X = dichloro, or dithiolate ligands) complexes and their interactions with an electron acceptor or Lewis acid. Chapter 3 assesses the use of some of these complexes in dye sensitized solar cells (DSSCs); it is shown that these complexes may lead to a viable …
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Synthetic models of [FeFe]-hydrogenase: case studies utilizing azadithiolate and nitrosyl coligands
… stable when the anion is BArF4-, where adt = (azadithiolate, (SCH2)2NR), R = H and CH2C6H5, BArF4- = tetrakis(bis(3,5-trifluoromethyl)phenyl)borate, and dppv = cis-1,2-bis(diphenylphosphino)ethylene). Solutions of [Fe2(adtR)(CO)3(PMe3)(dppv)]+ react with high pressures of H2 to give the hydride …
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Molecular electrocatalysis of hydrogen evolution: catalytic design studied by density functional theory
… Co(mnt)2 (mnt = maleonitrile-2,3-dithiolate), required the most overpotential for hydrogen evolution catalysis, despite having the most strongly electron-withdrawing substituents in the series and having produced hydrogen with the highest turnover frequency photochemically. The …
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