Electronic structure and spectroscopic properties of chromium(V), molybdenum(VI) and niobium(V) tetraperoxides

Roch, Michel; Weber, Jacques; Williams, A. F.

doi:10.1021/ic00194a034

Cited by 34 publications

(9 citation statements)

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“…Finally, both a large disruption of ligand T and T * levels and a shift towards lower energies of all the valence levels have been recently found in a series of tetraperoxo metal complexes to be possible indicators as to an enhanced reactivity of the system (24). 'The present results suggest that this statement could also apply to organometallic complexes with arene or condensed arene ligands.…”

Section: Methodssupporting

confidence: 66%

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

Weber¹,

Kündig²,

Goursot³

et al. 1985

Can. J. Chem.

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. SCF MS X a molecular orbital calculations are reported for the bis(q"benzene)-and bis(q6-naphthalene)chromium (O) complexes. The bonding may be essentially discussed in terms of the covalent interactions between the metal 3d and ligand .rr and .rr* orbitals. The different charges on chromium atom in the two systems are explained by the different balances between ligand-to-metal (bonding) and metal-to-ligand (back-bonding) electron donations. Some resemblances are found between the electronic structures of the two compounds and it is possible to correlate to a large extent the energy levels of their molecular orbitals. However, a shift towards lower values is predicted for the energy levels of the naphthalene complex, together with a large disruption of all the virtual .rr* and 3d* levels. This would undoubtedly favor nucleophilic attack followed by metal-ring or carbon-carbon bond cleavage, in agreement with the extreme lability of the coordinated arene rings observed in this complex.JACQUES WEBER, E. PETER KUNDIG, ANNICK GOURSOT et EDOUARD PENIGAULT. Can. J. Chem. 63, 1734Chem. 63, (1985.On a effectuC des calculs d'orbitales molCculaires MS Xa en champ autocohCrent pour les complexes bis(q"benzkne)-et bis(q6-naphtal&ne)chrome(0). On peut decrire la liaison dans le complex presque essentiellement l'aide des interactions covalentes entre les orbitales 3d du metal et les orbitales T et T* du ligand. On explique les diffkrentes charges sur l'atome de chrome dans les deux systemes par des bilans differents entre la donation directe d'klectrons ligand-mCtal et la rCtrodonation mCtal-ligand. Toutefois, on prCdit un dkplacement vers des valeurs plus basses pour les niveaux CnergCtiques du complexe de naphtalene ainsi qu'un mClange important de tous les niveaux virtuels .rr* et 3d*. Ceci devrait de toute evidence favoriser une attaque nuclCophile, suivie d'une rupture de la liaison mCtal-cycle ou carbone-carbone, en accord avec la labilitC extrCme observke dans ces complexes pour les cycles areniques coordonnCs.[Traduit par le journal]

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Section: Methodssupporting

confidence: 66%

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

Weber¹,

Kündig²,

Goursot³

et al. 1985

Can. J. Chem.

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“…The medium to strong bands at approximately 985, 836, 818, 781, 675, 590, 523, and 446 cm −1 for 1a, 955, 832, 797, 674, 585, 529, and 441 cm −1 for 2a are ascribed to the antisymmetric stretching vibrations of the terminal TaO bonds and the TaOTa bridges, respectively. The two obvious differences in IR spectra of 1a, 2a and Ta 6 are the appearance of bands at 850 cm −1 and strong intensity peaks in the regions 1200−1000 cm −1 (Figure 6), which originate from the peroxo group and PO bond, 48,49 respectively. This agrees well with the solid-state structure.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Discovery of Heteropolytantalate: Synthesis and Structure of Two 6-Peroxotantalo-4-phosphate Clusters

et al. 2017

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Polyoxometalates (POMs) of Nb and Ta are greatly different from those of Mo, W, and V that have been studied extensively and developed well. The latter can be formed simply by acidification of their aqueous monomeric oxoanions and has found application areas from catalysis to magnetism, materials science, medicine, and nanotechnology. Even now the polyoxoniobate (PONb) chemistry has accelerated dramatically over the last 15 years, and a vast expansion of available PONbs has been reported. However, after nearly 200 years of POM research, Ta-based POM chemistry is still at its infant stage and only dominated by the isopolyoxotantalate ions (Ta and Ta) and transition-metal-capped Ta species, along with two Ti-substituted polyoxotantalates [TiTaO] and [TiTaO] reported very recently. In this study, we discover two novel peroxotantalophosphate clusters [P(TaO)O] (1) and [P(TaO)O] (2) by incorporating phosphorus heteroatom into Ta-oxo framework, which represent the first two examples of heteropolytantalate. Interestingly, two PTa half-units are cis- and trans-condensed in 1 and 2, leading to "open" and "closed" configurations, respectively. These two chemically and structurally related clusters can be isolated in a controlled manner, and the yields are relatively high. Both compounds were characterized in the solid state by single-crystal X-ray diffraction, P MAS NMR, FT-IR, TGA, and elemental analysis as well as byP NMR in solution. The results presented here provide a strategy to be applicable to other heteroatom-incorporated polyoxotantalates and further expand the phase space for polyoxotantalate chemistry.

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“…This η 2 -peroxo-containing distorted pentagonal bipyramidal coordination polyhedron is seen for the metal centers in only one other conventional (highly condensed) polyoxoanion, the β 3 -[(Co II O 4 )W 11 O 31 (O 2 ) 4 ] 10- complex of Baker and co-workers. , None of the other structurally characterized polyperoxotungstates or polyperoxomolybdates have a conventional polyoxometalate structure. , The average O p −O p distance in 1 (1.43 Å) is slightly shorter than that for noncoordinated O 2 2- (1.49 Å) and is mainly attributed to the decrease in repulsion between the lone electron pairs on each oxygen in O 2 2- . The average Nb−O p distance of 1.93 Å is 0.1 Å shorter than that in the monomeric tetraperoxo niobium complex, [Nb(O 2 ) 4 ] 3- , , while the average O p −Nb−O p angle of 43.7° is close to that in [Nb(O 2 ) 4 ] 3- (43.3°). The relative orientations of the NbO 2 units at the belt positions is noteworthy; two of them (Nb8,O19,O20 and Nb14,O51,O52) lie in the plane defined by the W 4 Nb 2 belts, while the other two (Nb9,O21,O22 and Nb15,O53,O54) lie perpendicular.…”

mentioning

confidence: 82%

Synthesis, Solution and Solid State Structures, and Aqueous Chemistry of an Unstable Polyperoxo Polyoxometalate: [P₂W₁₂(NbO₂)₆O₅₆]¹²^-

et al. 1997

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Electronic structure and spectroscopic properties of chromium(V), molybdenum(VI) and niobium(V) tetraperoxides

Cited by 34 publications

References 2 publications

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

Discovery of Heteropolytantalate: Synthesis and Structure of Two 6-Peroxotantalo-4-phosphate Clusters

Synthesis, Solution and Solid State Structures, and Aqueous Chemistry of an Unstable Polyperoxo Polyoxometalate: [P₂W₁₂(NbO₂)₆O₅₆]¹²^-

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Electronic structure and spectroscopic properties of chromium(V), molybdenum(VI) and niobium(V) tetraperoxides

Cited by 34 publications

References 2 publications

The electronic structures of bis(η6-benzene)- and bis(η6-naphthalene)chromium(0)

The electronic structures of bis(η6-benzene)- and bis(η6-naphthalene)chromium(0)

Discovery of Heteropolytantalate: Synthesis and Structure of Two 6-Peroxotantalo-4-phosphate Clusters

Synthesis, Solution and Solid State Structures, and Aqueous Chemistry of an Unstable Polyperoxo Polyoxometalate: [P2W12(NbO2)6O56]12-

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The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

The electronic structures of bis(η⁶-benzene)- and bis(η⁶-naphthalene)chromium(0)

Synthesis, Solution and Solid State Structures, and Aqueous Chemistry of an Unstable Polyperoxo Polyoxometalate: [P₂W₁₂(NbO₂)₆O₅₆]¹²^-