Metal dithiolene complexes in olefin addition and purification, small molecule adsorption, H2 evolution and CO2 reduction

Pitchaimani, Jayaraman; Ni, Shao‐Fei; Dang, Li

doi:10.1016/j.ccr.2020.213398

Cited by 37 publications

(28 citation statements)

References 104 publications

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“…Examples include the active sites of redox-active metalloproteins, [1][2][3][4][5][6][7] many processes in the chemical industry, environmentally relevant transformations such as CO 2 -sequestration [8][9][10][11] and various types of small molecule activation of critical importance for renewable energy technologies such as H 2 O oxidation, [7,[12][13][14][15] N 2 reduction [16][17][18][19][20][21] and H 2 utilisation. [22][23][24][25][26][27][28][29] Consequently, understanding the interplay of redox transitions and chemical modifications in utmost detail is important, particularly when aiming to design and tune catalysts, or control and optimise chemical processes.…”

Section: Introductionmentioning

confidence: 99%

TowardsoperandoIR‐ and UV‐vis‐Spectro‐Electrochemistry: A Comprehensive Matrix Factorisation Study on Sensitive and Transient Molybdenum and Tungsten Mono‐Dithiolene Complexes**

et al. 2020

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The redox sequences of sensitive aliphatic mono-dithiolene complexes [M II (CO) 2 (cydt)(dppe)] (M = Mo, W) were studied with extensive cyclic voltammetrical and spectro-electrochemical (SEC) investigations using UV-vis and IR spectroscopy. With a newly developed matrix factorisation technique, the pure component spectra and temporal evolution of the developed species were ascertained, including sensitive and transient ones. The concentration of all involved compounds at the working electrode as dependent on the respective applied potential was derived with very high accuracy. The assignment of the species' geometries and electronic structures was further verified by quantum chemical calculations. Overall, the combined electrochemical, spectroscopic, quantum chemical and mathematical approach facilitates a comprehensive understanding of the underlying electrochemical transformations and equilibria. Since only a single CV run is needed to obtain all data required to identify the individual species, the method presented here is expected to be applicable to a wide range of complicated electrochemically responsive systems and thus opens a path towards developing a deeper mechanistic understanding of the underlying chemistry.

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Section: Introductionmentioning

confidence: 99%

TowardsoperandoIR‐ and UV‐vis‐Spectro‐Electrochemistry: A Comprehensive Matrix Factorisation Study on Sensitive and Transient Molybdenum and Tungsten Mono‐Dithiolene Complexes**

et al. 2020

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“…The sulfur-centered nucleophilic character of the dithiolene ligand can also support the reversible binding of olefins. In the process, the olefin double bond is broken and the reaction is reminiscent of typical cycloadditions (Figure 15e,f) [169,175]. The first examples of olefin reactivity were reported for nickel bis(dithiolene) complexes and strained (hence pre-activated) cyclic alkenes were applied [179][180][181].…”

Section: Non-catalytic Reactivity Toward Small Moleculesmentioning

confidence: 96%

“…Dithiolene chemistry was never restricted to biological issues, though, and these fascinating ligands and their coordination compounds continued to be extensively used for chemical purposes, and in particular for reactions in which their special redox modulating properties were anticipated or found to be advantageous. Consequently, dithiolene compounds are widely used with quite some versatility for often interdisciplinary scientific research topics, such as conducting materials, magnetism, MOF chemistry (including small molecule adsorption), gas sensor technique, or optical devices [163][164][165][166][167][168][169].…”

Section: Functional Dithiolene-bearing Analogues With Atypical/non-na...mentioning

confidence: 99%

“…One option in this regard is the utilization of homogenous transition metal catalysts coordinated, for instance, by non-innocent dithiolene ligands. The dithiolene ligands are presumed to participate in some extended electron relay events, thereby supporting the redox activity at the metal center [169]. Fontecave and others introduced several bioinspired molybdenum, tungsten-and cobalt-dependent dithiolene (qpdt, dmed, mnt) complexes, which exhibit electrocatalytic and photocatalytic activity toward hydrogen production (already discussed above as unwanted side reactions) [78,[170][171][172].…”

Section: Catalytic Hydrogen Evolution Reaction (Her)mentioning

confidence: 99%

“…Non-Catalytic Reactivity toward Small Molecules (Bio-)inorganic chemists on their quest towards unravelling the secrets of molybdenum and tungsten dithiolene chemistry, have to be aware that they may encounter unpredicted and rather surprising reactivities going back to the non-innocence character of the dithiolene. The inherent sulfur-based nucleophilic potential of the ligand can lead to a ligand-based, instead of a metal-based, reactivity [36,169,175]. Elvers et al, when examining the molybdenum mono(dithiolene) complex [Mo(CO) 2 (dt)(dppe)] (dt: cydt = cyclohex-1-ene-1,2-dithiolate or tpydt = 5,6-dihydro-2H-thiopyran-3,4-dithiolate; dppe = 1,2-bis(diphenylphosphino)ethane), noted and proved an unforeseen reactivity towards dichloromethane solvent upon electrochemical 2-electron reduction.…”

Section: Non-catalytic Reactivity Toward Small Moleculesmentioning

confidence: 99%

See 2 more Smart Citations

Inspired by Nature—Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases

et al. 2022

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Throughout the previous ten years many scientists took inspiration from natural molybdenum and tungsten-dependent oxidoreductases to build functional active site analogues. These studies not only led to an ever more detailed mechanistic understanding of the biological template, but also paved the way to atypical selectivity and activity, such as catalytic hydrogen evolution. This review is aimed at representing the last decade’s progress in the research of and with molybdenum and tungsten functional model compounds. The portrayed systems, organized according to their ability to facilitate typical and artificial enzyme reactions, comprise complexes with non-innocent dithiolene ligands, resembling molybdopterin, as well as entirely non-natural nitrogen, oxygen, and/or sulfur bearing chelating donor ligands. All model compounds receive individual attention, highlighting the specific novelty that each provides for our understanding of the enzymatic mechanisms, such as oxygen atom transfer and proton-coupled electron transfer, or that each presents for exploiting new and useful catalytic capability. Overall, a shift in the application of these model compounds towards uncommon reactions is noted, the latter are comprehensively discussed.

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Self‐Assembled Lithiophilic Interface with Abundant Nickel‐Bis(Dithiolene) Sites Enabling Highly Durable and Dendrite‐Free Lithium Metal Batteries

Wang,

Ke,

Qiao

et al. 2023

Advanced Energy Materials

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Despite its ultrahigh theoretical capacity and ultralow redox electrochemical potential, the practical application of lithium metal anodes is still hampered by severe dendrite growth and unstable solid electrolyte interphase (SEI). Herein, a self‐assembled lithiophilic interface (SALI) for regulating Li electroplating behavior is constructed by introducing a meticulously synthesized Ni‐bis(dithiolene)‐based molecule (NiS4‐COOH) into a hybrid fluorinated ester‐ether electrolyte. The NiS4‐COOH molecules with carboxyl functional groups can spontaneously anchor on the Li metal surface to form a SALI, whose abundant Ni‐bis(dithiolene) sites can effectively reduce the initial Li deposition overpotential and guide the subsequent uniform Li electrodeposition. Moreover, due to the interaction between the coordination unsaturated Ni atom and the negatively charged PF6−, the NiS4‐COOH additive can significantly change the ionic coordination environment in the electrolyte, which is greatly conducive to suppressing PF6− decomposition, optimizing SEI composition and accelerating Li‐ion transfer. Consequently, the NiS4‐COOH‐modified electrolyte leads to impressive electrochemical performance of Li||LiFePO4 and Li||LiNi0.8Co0.1Mn0.1O2 batteries, delivering ultrahigh Coulombic efficiencies, considerable capacity retention, and good rate performance even at high areal active material loadings. This study presents the great potential of SALIs derived from multifunctional metal‐organic hybrid electrolyte additives toward high‐specific‐energy Li metal batteries.

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Metal dithiolene complexes in olefin addition and purification, small molecule adsorption, H2 evolution and CO2 reduction

Cited by 37 publications

References 104 publications

TowardsoperandoIR‐ and UV‐vis‐Spectro‐Electrochemistry: A Comprehensive Matrix Factorisation Study on Sensitive and Transient Molybdenum and Tungsten Mono‐Dithiolene Complexes**

TowardsoperandoIR‐ and UV‐vis‐Spectro‐Electrochemistry: A Comprehensive Matrix Factorisation Study on Sensitive and Transient Molybdenum and Tungsten Mono‐Dithiolene Complexes**

Inspired by Nature—Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases

Self‐Assembled Lithiophilic Interface with Abundant Nickel‐Bis(Dithiolene) Sites Enabling Highly Durable and Dendrite‐Free Lithium Metal Batteries

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