Chemical bonding of hydrogen molecules to transition metal complexes

Kubas, Gregory J.

doi:10.1016/0022-5088(91)90168-4

Cited by 15 publications

(2 citation statements)

References 28 publications

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“…Correspondingly, the HÀH stretch frequency gets significantly red-shifted, close to the values around ñ = 2400-2800 cm À1 known from dihydrogen complex chemistry. [15,16] In summary, we have conclusively identified both dissociative hydride and non-dissociative dihydrogen species at the RuO 2 (110) surface. Although we find strong similarities for both types of species with data from transition-metal complex chemistry, the major difference is that with the surface both atomic and molecular hydrogen types are related to different sites: the dissociated b state to O bridge and the molecular a state to Ru cus atoms.…”

Section: Methodsmentioning

confidence: 86%

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110)

et al. 2003

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Similarities between bond formation in transition metal complexes and chemisorption on solid surfaces form the basis of the relationship between homogeneous and heterogeneous catalysis. We find that hydrogen interacts in a complicated manner with the two sites that have an incomplete coordination environment-Ru cus and O bridge -on the RuO 2 (110) surface (Figure 1). Upon exposure at 85 K of the RuO 2 catalyst to hydrogen gas, a H 2 molecule, instead of dissociating at Ru cus , weakly adsorbs as dihydrogen on top of the Ru cus atom and interacts dissociatively with the O bridge atom to form a metastable dihydride (waterlike) complex, which transforms into the stable monohydride when heated further. The combination of low-temperature ultrahigh vacuum experiments in conjunction with density-functional theory (DFT) calculations provides a detailed insight into the coordination chemistry of a solid surface, which exhibits a remarkable correlation with the chemistry of single-atom transition-metal complexes. The binding of hydrogen, both with transition-metal complexes (i.e. hydride formation) [1] and with surfaces, [2] generally occurs concurrently with dissociation of the ligand. The discovery of h 2 -H 2 (dihydrogen) complexes, in which the HÀH bond remains intact, was surprising, [3] since

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Section: Methodsmentioning

confidence: 86%

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110)

et al. 2003

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“…In all cases so far, density functional theory (DFT) has been used in these studies. Various aspects of the hydrogenase enzymes have been the subject of a number of recent reviews. − The activation of dihydrogen by discrete, synthetic transition-metal complexes has also been the subject of a number of excellent reviews. − …”

Section: Introductionmentioning

confidence: 99%

Computational Studies of [NiFe] and [FeFe] Hydrogenases

2007

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An Übergangsmetalle koordinierte σ‐Bindungen

Crabtree

1993

Angewandte Chemie

129

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Die ersten σ‐Komplexe wurden in den sechziger und siebziger Jahren entdeckt, doch sie erregten nur vorübergehend Interesse. Erst seit kurzem beginnt man, ihre Schlüsselrolle bei chemischen Reaktionen von ‐Bindungen zu begreifen; dies hat Anlaß zu detaillierteren Untersuchungen gegeben. Im Gegensatz zu den vertrauteren ‐Donorkomplexen wie M(H2C=CH2) oder Komplexen wie M‐NH3, bei denen das freie Elektronenpaar am N‐Atom das Metallatom bindet, koordiniert bei ‐Komplexen eine X‐H‐Gruppe mit dem X‐H‐Bindungselektronenpaar als 2e‐Donor an das Übergangsmetallatom. Dabei entstehen Komplexe vom Typ (X‐H)‐M; eine wichtige Gruppe der σ‐Komplexe sind Diwasserstoffkomplexe (X = H). C‐H‐M‐Komplexe mit agostischer Wechselwirkung (X = R3C) wurden nicht nur im Grundzustand beobachtet, sondern sie sind auch an der Übergangszuständen vieler wichtiger metallorganischer Umsetzungen, beispielsweise der Ziegler‐Natta‐Katalyse und der σ‐Metathese, beteiligt. Das allgemeine Problem der X‐H‐Bindungsaktivierung wird die Entwicklung auf diesem Gebiet vorantreiben.

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Chemical bonding of hydrogen molecules to transition metal complexes

Cited by 15 publications

References 28 publications

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110)

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110)

Computational Studies of [NiFe] and [FeFe] Hydrogenases

An Übergangsmetalle koordinierte σ‐Bindungen

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Chemical bonding of hydrogen molecules to transition metal complexes

Cited by 15 publications

References 28 publications

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO2(110)

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO2(110)

Computational Studies of [NiFe] and [FeFe] Hydrogenases

An Übergangsmetalle koordinierte σ‐Bindungen

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Product

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Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110)

Surface Coordination Chemistry: Dihydrogen versus Hydride Complexes on RuO₂(110)