<b>Activation of Hydrogen by a Transition Metal Complex at Normal Conditions Leading to a Stable Molecular Dihydride</b>

Vaska, L.; DiLuzio, John W.

doi:10.1021/ja00863a040

Cited by 206 publications

(92 citation statements)

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“…In 1984, Kubas et al [136] synthesized the first TM complex with an H 2 ligand, the yellow W(CO) 3 (η 2 -H 2 ){P(C 6 H 11 ) 3 } 2 , by precipitating it from a toluene solution of W(CO) 3 {P(C 6 H 11 ) 3 } 2 with H 2 gas. An example of hydride formation is Ir(CO)Cl(H) 2 {P(C 6 H 5 ) 3 } 2 [137,138], obtained from H 2 and the square-planar Ir(CO)Cl{P(C 6 H 5 ) 3 } 2 , aka Vaska's complex [139]. Only the latter reaction is an oxidative addition.…”

Section: Dihydrogen-and Hydrido Complexesmentioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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Section: Dihydrogen-and Hydrido Complexesmentioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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“…trans-~~alocarbonylbis(triphenylphosphine) iridiutn(I), IrX(C0) (Ph,P), These complexes were prepared according to literature procedures (4,16).…”

Section: Experimental (I) Materialsmentioning

confidence: 99%

A Kinetic Study of the Oxidative Addition of Substituted Benzenethiols Towards trans-Halocarbonylbis(triphenylphosphine)iridium(I)

Gaylor¹,

Senoff²

1972

Can. J. Chem.

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The kinetics of the oxidative addition of a series of para-substituted benzenethiols, HSC6H4Y, where Y = 4-NO,, 4-Br, 4-CI, 4-F, 4-H, 4-CH,, or 4-CH30 towards the complexes, rrans-IrX(CO)(Ph,P), where X = CI, Br, or I have been studied in benzene between 15 and 45". These reactions follow simple second order kinetics, rate = k2[IrX(CO)(Ph3P)2][HSC6H4Y]. The two principal factors which influence the rates of these reactions are the mesomeric and inductive effects of the para-substituent and the nature of the ligand, X, coordinated to iridium. The rate of reaction increases as the substituent becomes more electron withdrawing and as X varies from Cl to Br to I. The kinetic data together with spectroscopic data (i.r. and n.m.r.) suggest that oxidative addition proceeds via a three-centered activated complex to give the cis-product.

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“…Crystals suitable for X-ray analysis were grown from slow evaporation from dichloromethane. 1 Geometries of the studied systems were optimized both in the gas phase as well as in solution (methylene chloride) using the PBE1PBE density functional [43][44][45][46] in combination with Ahlrichs' TZVP basis sets. 47 The polarizable continuum model, as implemented in Gaussian 09, was used for the treatment of solvent effects.…”

Section: Synthesis Ofmentioning

confidence: 99%

Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles

et al. 2013

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ABSTRACT:The perfluoro and perprotiopentaphenyl boroles 1 and 2 react with dihydrogen to effect H-H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H2. The reaction is first order in both . A minimal kinetic isotope effect of 1.10(5) was observed, suggesting rate limiting binding of H2 to the boron center of the borole. To explain the stereochemistry of the observed products, a ring-opening/ring-closing mechanism is proposed and supported by the separate synthesis of a proposed intermediate and its observed conversion to product. Furthermore, extensive DFT mapping of the reaction mechanism supports the plausibility of this proposal. The study illustrates a new mechanism for the activation of H2 by a strong main group Lewis acid in the absence of an external base, a process driven in part by the antiaromaticity of the borole rings in 1 and 2.

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Activation of Hydrogen by a Transition Metal Complex at Normal Conditions Leading to a Stable Molecular Dihydride

Cited by 206 publications

References 0 publications

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

A Kinetic Study of the Oxidative Addition of Substituted Benzenethiols Towards trans-Halocarbonylbis(triphenylphosphine)iridium(I)

Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles

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