Heterodinuclear Ni/M (M = Mo, W) Complexes Relevant to the Active Site of [NiFe]-Hydrogenases: Synthesis, Characterization, and Electrocatalytic H<sub>2</sub> Evolution

Song, Li‐Cheng; Zhang, Long-Duo; Zhang, Weiwei; Liu, Beibei

doi:10.1021/acs.organomet.8b00228

Cited by 11 publications

(3 citation statements)

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“…Both the strength of M–W bonding and lowering of the W d exchange energy are enabled by the more diffuse d orbitals of the 5d transition metal . There are recent reports of heterobimetallic compounds with Ni–Mo and Ni–W bonds, but neither XAS spectroscopy nor computations were reported to explore the nature of these bonds. , In a more distantly related system, a computational study compared the exchange interactions in linear Ni 3 , Ni 2 Pd, and Pd 3 complexes, demonstrating that the more diffuse d orbitals of Pd compared to Ni resulted in stronger antiferromagnetic coupling. As in the system here, the coupling was mediated by increased M–M σ-bonding interactions as well as lowered intrasite exchange that stabilized local non-Hund configurations. , Increased M–M covalency was also found in a study of the FeMo vs FeV cofactors of nitrogenase as well as MoFe 3 vs VFe 3 model clusters .…”

Section: Discussionmentioning

confidence: 99%

Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster

Wilson,

Fataftah,

Mathe

et al. 2024

J. Am. Chem. Soc.

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Biological multielectron reactions often are performed by metalloenzymes with heterometallic sites, such as anaerobic carbon monoxide dehydrogenase (CODH), which has a nickel–iron–sulfide cubane with a possible three-coordinate nickel site. Here, we isolate the first synthetic iron–sulfur clusters having a nickel atom with only three donors, showing that this structural feature is feasible. These have a core with two tetrahedral irons, one octahedral tungsten, and a three-coordinate nickel connected by sulfide and thiolate bridges. Electron paramagnetic resonance (EPR), Mössbauer, and superconducting quantum interference device (SQUID) data are combined with density functional theory (DFT) computations to show how the electronic structure of the cluster arises from strong magnetic coupling between the Ni, Fe, and W sites. X-ray absorption spectroscopy, together with spectroscopically validated DFT analysis, suggests that the electronic structure can be described with a formal Ni1+ atom participating in a nonpolar Ni–W σ-bond. This metal–metal bond, which minimizes spin density at Ni1+, is conserved in two cluster oxidation states. Fe–W bonding is found in all clusters, in one case stabilizing a local non-Hund state at tungsten. Based on these results, we compare different M–M interactions and speculate that other heterometallic clusters, including metalloenzyme active sites, could likewise store redox equivalents and stabilize low-valent metal centers through metal–metal bonding.

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Section: Discussionmentioning

confidence: 99%

Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster

Wilson,

Fataftah,

Mathe

et al. 2024

J. Am. Chem. Soc.

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“…Homoleptic Group 10 metal complexes were prepared, as their tetrafluoroborate salts, and the Pd/Pt complexes were shown to be extremely potent complexes for CSC mammosphere activity. Additional functionalities have been incorporated into the -N(R)-backbone (2c, 2d) and, in these cases, no further donor atom participation was found in the resulting complexes that were studied [36,37]. Khan and co-workers have used some simple, -N(aryl)-modified, (diphosphino)amines to investigate a range of Au(I) complexes and their aurophilic behaviour [38].…”

Section: Synthesis Of Selected Examplesmentioning

confidence: 99%

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Smith

2022

Molecules

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Organophosphorus ligands are an invaluable family of compounds that continue to underpin important roles in disciplines such as coordination chemistry and catalysis. Their success can routinely be traced back to facile tuneability thus enabling a high degree of control over, for example, electronic and steric properties. Diphosphines, phosphorus compounds bearing two separated PIII donor atoms, are also highly valued and impart their own unique features, for example excellent chelating properties upon metal complexation. In many classical ligands of this type, the backbone connectivity has been based on all carbon spacers only but there is growing interest in embedding other donor atoms such as additional nitrogen (–NH–, –NR–) sites. This review will collate some important examples of ligands in this field, illustrate their role as ligands in coordination chemistry and highlight some of their reactivities and applications. It will be shown that incorporation of a nitrogen-based group can impart unusual reactivities and important catalytic applications.

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“…Inspired by the well-elucidated structure shown in Figure a, synthetic chemists have prepared a large number of the hetero- and homodinuclear Ni–M (M = Fe, Ru, Mn, Mo, W, Co, Ni, etc. )-based biomimetic mimics for [NiFe]-H 2 ases, but none of them contain the azadithiolato type of ligand. − Recently, considering that the bridging azadithiolato ligand in the active site of [FeFe]-H 2 ases can play a key role in the catalytic redox reaction between H 2 and protons − and in order to further develop the biomimetic chemistry of [NiFe]-H 2 ases, we decided to prepare the first azadithiolato ligand containing dinuclear Ni 2 complexes in which each of the azadithiolato 4-RC 6 H 4 N(CH 2 S) 2 ligands is bridged between the two Ni atoms in CpNi and (diphosphine)Ni moieties (Figure b). Fortunately, we have successfully synthesized and structurally characterized such a type of dinuclear Ni 2 complex and in particular some of them have been found to be catalysts for proton reduction to H 2 under CV conditions.…”

Section: Introductionmentioning

confidence: 99%

Nickel(II)–Nickel(II) Azadithiolates: Synthesis, Structural Characterization, and Electrocatalytic H₂ Production

Song

Liu

2020

Organometallics

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Azadithiolato-bridged dinuclear Ni2 complexes with the general formula [(η5-C5H5)Ni{(μ-SCH2)2NC6H4R-4}Ni(diphos)]BF4 (8–11, R = H, Cl, MeO; diphos = dppv, dppe) have been prepared by a well-designed synthetic method including the following three separate reaction steps. The first reaction step involves preparation of the bis(thioester) precursors 4-RC6H4N(CH2S(O)CMe)2 (1–3, R = H, Cl, MeO) by a cocondensation reaction of aniline or its substituted derivatives 4-RC6H4NH2 with 37% aqueous formaldehyde and thioacetic acid. The second step involves preparation of the mononuclear Ni precursors (diphos)Ni[(SCH2)2NC6H4R-4] (4–7, R = H, Cl, MeO; diphos = dppv, dppe) by a one-pot reaction of bis(thioester) precursors 1–3 with t-BuONa followed by treatment of the resulting disodium intermediates 4-RC6H4N(CH2SNa)2 with (dppv)NiCl2 and (dppe)NiCl2, respectively. The third step involves preparation of the targeted dinuclear Ni2 complexes 8–11 by coordination reactions of mononuclear Ni precursors 4–7 with [η5-C5H5Ni]+ generated in situ from dissociation of the triple-decker sandwich complex [(C5H5)3Ni2]BF4. While all of the prepared compounds 1–11 have been characterized by elemental analysis and various spectroscopic techniques, the molecular structures of precursor complex 5 and targeted complexes 9 and 11 have been further confirmed by X-ray crystallography. In addition, the two representative targeted complexes 8 and 9 have been found to be catalysts for proton reduction to hydrogen using acetic acid as the proton source under electrochemical conditions.

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Heterodinuclear Ni/M (M = Mo, W) Complexes Relevant to the Active Site of [NiFe]-Hydrogenases: Synthesis, Characterization, and Electrocatalytic H₂ Evolution

Cited by 11 publications

References 73 publications

Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster

Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Nickel(II)–Nickel(II) Azadithiolates: Synthesis, Structural Characterization, and Electrocatalytic H₂ Production

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Heterodinuclear Ni/M (M = Mo, W) Complexes Relevant to the Active Site of [NiFe]-Hydrogenases: Synthesis, Characterization, and Electrocatalytic H2 Evolution

Cited by 11 publications

References 73 publications

Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster

Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Nickel(II)–Nickel(II) Azadithiolates: Synthesis, Structural Characterization, and Electrocatalytic H2 Production

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Product

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Heterodinuclear Ni/M (M = Mo, W) Complexes Relevant to the Active Site of [NiFe]-Hydrogenases: Synthesis, Characterization, and Electrocatalytic H₂ Evolution

Nickel(II)–Nickel(II) Azadithiolates: Synthesis, Structural Characterization, and Electrocatalytic H₂ Production