Heat of reaction of (norbornadiene)molybdenum tetracarbonyl with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the complexes cis-L2Mo(CO)4

Mukerjee, Shakti L.; Nolan, Steven P.; Hoff, Carl D.; Vega, R. Lopez De La

doi:10.1021/ic00274a018

Cited by 49 publications

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“…The complexes 1 , 2 and 3 were prepared following previously described procedures and characterized by 1 H NMR and IR spectroscopy (see Supplementary Information) [14a,b,e,15] . The solids were analyzed by solid state IR spectroscopy using an ATR detector.…”

Section: Resultsmentioning

confidence: 99%

Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

et al. 2021

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The activation of carbon dioxide by three different Mo-diimine complexes [Mo(CO) 4 (L)] (L = bipyridine (bpy), 1,10-phenantroline (phen) or pyridylindolizine (py-indz)) has been investigated by electrochemistry and spectroelectrochemistry. Under an inert atmosphere, monoreduction of the complexes is ligandcentered and leads to tetracarbonyl [Mo(CO) 4 (L)] * À species, whereas double reduction induces CO release. Under CO 2 , [Mo(CO) 4 (L)] complexes undergo unexpected coupled chemicalelectrochemical reactions at the first reduction step, leading to the formation of reduced CO 2 derivatives. The experimental results obtained from IR, NIR and UV-Vis spectroelectrochemistry, as well as DFT calculations, demonstrate an electron-transfer reaction whose rate is ligand-dependent.

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Section: Resultsmentioning

confidence: 99%

Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

et al. 2021

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“…This series of stoichiometric reactions could not be rendered catalytic using CO(g) due to strong inhibition of the catalyst by excess CO. However, turnover could be achieved using Cr(CO) 6 , which slowly releases free CO at high temperatures. Under optimized conditions, several catalytic carbonylative rearrangements were carried out using 7-substituted norbornadienes as substrates.…”

Section: Stoichiometric Reactivity and Catalysismentioning

confidence: 99%

Dinickel Active Sites Supported by Redox-Active Ligands

Uyeda

Farley

2021

Acc. Chem. Res.

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Conspectus Redox reactions that take place in enzymes and on the surfaces of heterogeneous catalysts often require active sites that contain multiple metals. By contrast, there are very few homogeneous catalysts with multinuclear active sites, and the field of organometallic chemistry continues to be dominated by the study of single metal systems. Multinuclear catalysts have the potential to display unique properties owing to their ability to cooperatively engage substrates. Furthermore, direct metal-to-metal covalent bonding can give rise to new electronic configurations that dramatically impact substrate binding and reactivity. In order to effectively capitalize on these features, it is necessary to consider strategies to avoid the dissociation of fragile metal–metal bonds in the course of a catalytic cycle. This Account describes one approach to accomplishing this goal using binucleating redox-active ligands. In 2006, Chirik showed that pyridine–diimines (PDI) have sufficiently low-lying π* levels that they can be redox-noninnocent in low-valent iron complexes. Extending this concept, we investigated a series of dinickel complexes supported by naphthyridine–diimine (NDI) ligands. These complexes can promote a broad range of two-electron redox processes in which the NDI ligand manages electron equivalents while the metals remain in a Ni(I)–Ni(I) state. Using (NDI)Ni2 catalysts, we have uncovered cases where having two metals in the active site addresses a problem in catalysis that had not been adequately solved using single-metal systems. For example, mononickel complexes are capable of stoichiometrically dimerizing aryl azides to form azoarenes but do not turn over due to strong product inhibition. By contrast, dinickel complexes are effective catalysts for this reaction and avoid this thermodynamic sink by binding to azoarenes in their higher-energy cis form. Dinickel complexes can also activate strong bonds through the cooperative action of both metals. Norbornadiene has a ring-strain energy that is similar to that of cyclopropane but is not prone to undergoing C–C oxidative addition with monometallic complexes. Using an (NDI)Ni2 complex, norbornadiene undergoes rapid ring opening by the oxidative addition of the vinyl and bridgehead carbons. An inspection of the resulting metallacycle reveals that it is stabilized through a network of secondary Ni−π interactions. This reactivity enabled the development of a catalytic carbonylative rearrangement to form fused bicyclic dienones. These vignettes and others described in this Account highlight some of the implications of metal–metal bonding in promoting a challenging step in a catalytic cycle or adjusting the thermodynamic landscape of key intermediates. Given that our studies have focused nearly exclusively on the (NDI)Ni2 system, we anticipate that many more such cases are left to be discovered as other transition-metal combinations and ligand classes are explored.

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“…This is often done with acetonitrile, which results in fac-[Mo(CH 3 CN) 3 (CO) 3 ] complexes. Other examples comprise, for instance, [Mo(CO) 5 (THF)] (THF = tetrahydrofurane), [Mo(CO) 4 (nbd)] (nbd = norbornadiene) and fac-[Mo(CO) 3 (DMF) 3 ] (DMF = dimethyl formamide) (Wieland & van Eldik, 1991;Mukerjee et al 1988;Villanueva et al, 1996). Depending on the co-ligand, the stability and reactivity of the resultant complex can be fine-tuned.…”

Section: Chemical Contextmentioning

confidence: 99%

Molecular structure of fac-[Mo(CO)₃(DMSO)₃]

Elvers¹,

Fischer²,

Schulzke³

2021

Acta Cryst E

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The title compound, tricarbonyltris(dimethyl sulfoxide)molybdenum, [Mo(C2H6OS)3(CO)3] or fac-[Mo(CO)3(DMSO)3], crystallizes in the triclinic space group P\overline{1} with two molecules in the unit cell. The geometry around the central molybdenum is slightly distorted octahedral and the facial isomer is found exclusively. The packing within the crystal is stabilized by three-dimensional non-classical intermolecular hydrogen-bonding contacts between individual methyl substituents of dimethyl sulfoxide and the oxygen atoms of either another dimethyl sulfoxide or a carbonyl ligand on adjacent complex molecules. The observed bond lengths in the carbonyl ligands and between carbonyl carbon atoms and molybdenum are correlated to the observed FT–IR bands for the carbonyl stretches and compared to respective metrical parameters of related complexes.

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Heat of reaction of (norbornadiene)molybdenum tetracarbonyl with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the complexes cis-L2Mo(CO)4

Cited by 49 publications

References 0 publications

Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

Dinickel Active Sites Supported by Redox-Active Ligands

Molecular structure of fac-[Mo(CO)₃(DMSO)₃]

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Heat of reaction of (norbornadiene)molybdenum tetracarbonyl with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the complexes cis-L2Mo(CO)4

Cited by 49 publications

References 0 publications

Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono‐Reduced Mo‐Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies

Dinickel Active Sites Supported by Redox-Active Ligands

Molecular structure of fac-[Mo(CO)3(DMSO)3]

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Molecular structure of fac-[Mo(CO)₃(DMSO)₃]