Vanadium and Niobium Hexadinitrogen and Hexacarbonyl Complexes:  Electron-Spin-Resonance Spectra at 4 K

Parrish, S. H.; Zee, and R. J. Van; Weltner, W.

doi:10.1021/jp983952o

Cited by 30 publications

(38 citation statements)

References 25 publications

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“…[52] Side-on bonding of dinitrogen to Fe surfaces has been modelled, for example, by multiconfiguration self-consistent field CASSCF calculations. [53] In a more recent study, the role of defects in N 2 dissociation on Fe (110) and Fe/Ru(0001) surfaces has been analyzed. [54] Not surprisingly, it emerges that defects are of importance for the dissociation to take place.…”

Section: Transition Elementssupporting

confidence: 70%

“…[53] In a more recent study, the role of defects in N 2 dissociation on Fe (110) and Fe/Ru(0001) surfaces has been analyzed. [54] Not surprisingly, it emerges that defects are of importance for the dissociation to take place.…”

Section: Transition Elementsmentioning

confidence: 99%

“…The interaction of vanadium atoms with N 2 in pure N 2 matrices was analyzed with the aid of matrix-isolation experiments and by using IR, [108,109] ESR, [110] and UV/Vis [111] spectroscopy. These experiments give evidence for the complex [V(N 2 ) 6 ].…”

Section: Groupmentioning

confidence: 99%

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Intrinsic Dinitrogen Activation at Bare Metal Atoms

Himmel¹,

Reiher²

2006

Angew Chem Int Ed

119

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There is ongoing interest in metal complexes which bind dinitrogen and facilitate either its reduction or oxidation under mild conditions. In nature, the enzyme nitrogenase catalyzes this process, and dinitrogen fixation occurs under mild and ambient conditions at a metal-sulfur cluster in the center of the MoFe protein, but the mechanism of this process remains largely unknown. In the last few years, new important discoveries have been made in this field. In this review are discussed recent findings on the interaction of N(2) with metal atoms and metal-atom dimers from all groups of the periodic table as provided by gas-phase as well as matrix-isolation experiments. Intrinsic dinitrogen activation at such bare metal atoms is then related to corresponding processes at complexes, clusters, and surfaces.

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Section: Transition Elementssupporting

confidence: 70%

Section: Transition Elementsmentioning

confidence: 99%

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Intrinsic Dinitrogen Activation at Bare Metal Atoms

Himmel¹,

Reiher²

2006

Angew Chem Int Ed

119

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“…[4] Although Ta(bipy) 3 ,bipy = a,a'-bipyridine, [5] and Ta(iPr 2 -dad) 3 , iPr 2 -dad = 1,4-diisopropyl-1,4-diazabuta-1,3-diene, [6] were originally suggested to be zerovalent tantalum complexes,later experimental and computational studies indicate that both compounds contain high-valent Ta V . [7] Perhaps the most interesting comparisons of homoleptic zerovalent complexes of Group 5m etals are for the 17electron hexacarbonyls of these species:V (CO) 6 is wellknown as the only paramagnetic unsubstituted metal carbonyl isolable under ambient conditions, [8] while Ta(CO) 6 [9] and Nb(CO) 6 [10] have only been obtained at low temperatures as matrix isolated species and may be unstable above 50 K. Barybinss ynthesis of the 17-electron complex V(CNXyl) 6 , Xyl = 2,6-dimethylphenyl, which was far more thermally stable (m.p.1 59-160 8 8Cd ecomp.) [1i] than V(CO) 6 (decomp.…”

mentioning

confidence: 99%

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

et al. 2017

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Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly unstable Ta(CO) and represents the only well-defined zerovalent tantalum complex to be prepared by conventional laboratory methods. Two prior examples of homoleptic Ta complexes are known, Ta(benzene) and Ta(dmpe) , dmpe=1,2-bis(dimethylphosphano)ethane, but these have only been accessed via ligand co-condensation with tantalum vapor in a sophisticated metal-atom reactor. Consistent with its 17-electron nature, Ta(CNDipp) undergoes facile one-electron oxidation, reduction, or disproportionation reactions. In this sense, it qualitatively resembles V(CO) , the only paramagnetic homoleptic metal carbonyl isolable under ambient conditions.

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“…148 The X-ray data at À30 C indicated a small tetragonal distortion that may also be due to crystal packing effects. 150 The structures, relative energies, vibrational spectra, and ESR parameters were computed with DFTand high-level ab initio methods using different basis sets. V(CO) 6 exists in a CO matrix at 4K in axial symmetry (D 4h or D 3d ).…”

Section: Computational Studies Of Radical Systemsmentioning

confidence: 99%