Nature of the hydrogen bridge in transition metal complexes

Jeżowska‐Trzebiatowska, B.; Nissen-Sobocińska, Barbara

doi:10.1016/s0022-328x(00)99361-6

Cited by 22 publications

(2 citation statements)

References 23 publications

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“…Of particular interest is the existence and nature of the metal−metal multiple bond, together with its most characteristic structural manifestation, namely the metal−metal bond length. Along with optimization of the geometry, we compute the molecular coefficients and the energy levels for all the molecular orbitals (MOs), and analyze which d orbitals give the largest contributions . The symmetry-adapted linear combinations of the d atomic orbitals will provide the bonding and antibonding interactions between the metal atoms.…”

Section: Introductionmentioning

confidence: 99%

Chromium−Chromium Multiple Bonding in Cr₂(CO)₉

Richardson

King

et al. 2003

J. Phys. Chem. A

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Density functional theory (DFT) is used to obtain the first structural characterization of the unsaturated dichromium carbonyl Cr2(CO)9, which is predicted to have a remarkably short metal−metal bond length of 2.31 Å (B3LYP) or 2.28 Å (BP86). This chromium−chromium distance is essentially identical to that reported experimentally for the established Cr⋮Cr triple bond in (η5-Me5C5)2Cr2(CO)4. The dissociation energy to the fragments Cr(CO)4 and Cr(CO)5 is determined to be 32 kcal/mol (B3LYP) or 43 kcal/mol (BP86). For comparison, the Cr2(CO)10 molecule and the saturated Cr2(CO)11 system have negligible dissociation energies. The minimum energy Cr2(CO)9 structure is of C s symmetry with the two chromium atoms asymmetrically bonded to the bridging carbonyls. However, within 0.1 kcal/mol lies a C 2 symmetry structure with one symmetric and two asymmetric bridging carbonyls. Furthermore, the high symmetry D 3 h structure analogous to Fe2(CO)9 lies only ∼1 kcal/mol higher in energy. The Cr2(CO)9 molecule is thus highly fluxional. The extremely flat potential energy surface in the region adjacent to these minima suggests that Cr2(CO)9 will be labile. The relationship between the Cr2(CO)9 molecule and the experimentally known binuclear manganese (η5-Me5C5)2Mn2(μ-CO)3 compound is explored.

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Section: Introductionmentioning

confidence: 99%

Chromium−Chromium Multiple Bonding in Cr₂(CO)₉

Richardson

King

et al. 2003

J. Phys. Chem. A

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“…In order to understand the origin of the intense visible absorptions of the dimeric product, we have undertaken a DFT study of the electronic structure of this dimeric species. The electronic structure of transition metal complexes with bridging hydride ligands has previously been subjected to symmetry considerations and EHMO, , Fenske−Hall, and DFT calculations. , …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Electronic Properties of Monomeric and Dimeric Trispyrazolylborate Platinum(II) Hydride Complexes

et al. 2001

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Tp'PtMe(H)2 (2) [Tp' = hydridotris(3,5-dimethylpyrazolyl)borate] has been prepared from Tp'PtMe(CO) (1) via reaction with water in a basic acetone/water mixture. Protonation of 2 at one of the pyrazole nitrogen atoms induces methane elimination, and the resulting platinum(II) monohydride solvent intermediate (3) can be trapped by added ligand. Two chiral cationic platinum(II) monohydride complexes of the type [kappa(2)-((Hpz)BHpz2)Pt(H)(L)][BAr'4] [L = MeCN (4), CH2=CH2 (5); pz = 3,5-dimethylpyrazolyl, BAr'4 = tetrakis(3,5-trifluoromethylphenyl)borate] have been isolated. If 2 is protonated in the absence of trapping ligand, a deep red hydride-bridged dinuclear complex, [kappa(2)-((Hpz)BHpz2)Pt(mu-H)]2[BAr'4]2 (6), forms. DFT calculations supplement intuitive expectations regarding 3-center-2-electron bridging orbital descriptions for the electronic structure of this complex. X-ray structure determinations for the monomeric acetonitrile adduct 4 and the dicationic dimer 6 are reported.

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Bonding and Reactivity of a μ‐Hydrido Dicopper Cation

et al. 2013

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Ein gebogenes Dikupfer‐Hydrid‐Kation mit unterstützendem N‐heterocyclischem Carbenligand weist im Festkörper einen Cu‐H‐Cu‐Winkel von 122° auf. Dichtefunktionalrechnungen sprechen für eine offene Metall‐Wasserstoff‐Drei‐Zentren‐Wechselwirkung. Das Hydrid reagiert bereitwillig mit Methanol und Kohlendioxid, und durch Insertion von Phenylacetylen entsteht ein gem‐Dikupfer‐Vinylkomplex.

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Nature of the hydrogen bridge in transition metal complexes

Cited by 22 publications

References 23 publications

Chromium−Chromium Multiple Bonding in Cr₂(CO)₉

Chromium−Chromium Multiple Bonding in Cr₂(CO)₉

Synthesis, Structure, and Electronic Properties of Monomeric and Dimeric Trispyrazolylborate Platinum(II) Hydride Complexes

Bonding and Reactivity of a μ‐Hydrido Dicopper Cation

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Nature of the hydrogen bridge in transition metal complexes

Cited by 22 publications

References 23 publications

Chromium−Chromium Multiple Bonding in Cr2(CO)9

Chromium−Chromium Multiple Bonding in Cr2(CO)9

Synthesis, Structure, and Electronic Properties of Monomeric and Dimeric Trispyrazolylborate Platinum(II) Hydride Complexes

Bonding and Reactivity of a μ‐Hydrido Dicopper Cation

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Chromium−Chromium Multiple Bonding in Cr₂(CO)₉

Chromium−Chromium Multiple Bonding in Cr₂(CO)₉