DFT study of the reactivity of methane and dioxygen with d10-L2M complexes

Cundari, Thomas R.; Prince, Bruce M.

doi:10.1016/j.jorganchem.2011.06.015

Cited by 11 publications

(17 citation statements)

References 30 publications

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“…8 Methanol is used in the synthesis of several important chemicals: dimethyl ether, formaldehyde, acetic acid, etc. However, because methane is inert and possesses a large C−H bond dissociation enthalpy (BDE, ∼105 kcal/mol), it has been challenging to effect selective partial oxidation of methane to methanol.…”

Section: ■ Introductionmentioning

confidence: 99%

DFT Study of the Reaction of a Two-Coordinate Iron(II) Dialkyl Complex with Molecular Oxygen

2014

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DFT studies are reported of a monomeric iron dialkyl for which oxygen atom insertion into metal-methyl bonds occurs with O2: FeMe2 + O2 → Fe(OMe)2. Computation of the reaction coordinate implicates the intermediacy of Fe(III)-peroxo, Fe(VI)-dioxo, and Fe(IV)-oxo intermediates, connected by O2 oxidative addition and two methyl migration steps. Analysis of the reaction of O2 with d(6)-Fe(Me)2 indicates that oxy-insertion for this iron complex occurs with lower free energy barriers than competing homolytic/radical pathways, exploiting "spin-flip" processes via minimum energy crossing points (MECPs).

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Section: ■ Introductionmentioning

confidence: 99%

DFT Study of the Reaction of a Two-Coordinate Iron(II) Dialkyl Complex with Molecular Oxygen

2014

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“…[10] Based on the current state of research with respect to reactive d 10 -ML 2 systems, it seemed challenging to synthesize compounds by employing chelating bis-NHC ligands that enforce a cis configuration at the metal center. [11] Already in the first application of NHC complexes in homogeneous catalysis, bis-NHC chelate complexes of palladium(II) were studied. [12a] Complexes bearing this type of ligand are now established for most late transition metals in all prevalent oxidation states.…”

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confidence: 99%

“…Selected bond lengths [] and angles [8]: Ni-C1 1.905 (3), Ni-C6 1.921(4), Ni-C12 1.951(4), Ni-C13 1.955 (3), C12-C13 1.426 (5); C1-Ni-C6 91.00 (16). (6), Pt-C6 2.052 (6), Pt-C12 2.077 (6), Pt-C13 2.091 (6), C12-C13 1.468 (8); C1-Pt-C6 84.6 (2); chair (bottom): Pt-C1 2.065 (7), Pt-C6 2.052 (6), Pt-C12 2.072 (6), Pt-C13 2.082 (7), C12-C13 1.461 (11); C1-Pt-C6 83.7 (2).…”

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Bis‐NHC Chelate Complexes of Nickel(0) and Platinum(0)

et al. 2014

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For a long time d(10)-ML2 fragments have been known for their potential to activate unreactive bonds by oxidative addition. In the development of more active species, two approaches have proven successful: the use of strong σ-donating ligands leading to electron-rich metal centers and the employment of chelating ligands resulting in a bent coordination geometry. Combining these two strategies, we synthesized bis-NHC chelate complexes of nickel(0) and platinum(0). Bis(1,5-cyclooctadiene)nickel(0) and -platinum(0) react with bisimidazolium salts, deprotonated in situ at room temperature, to yield tetrahedral or trigonal-planar bis-NHC chelate olefin complexes. The synthesis and characterization of these complexes as well as a first example of C-C bond activation with these systems are reported. Due to the enforced cis arrangement of two NHCs, these compounds should open interesting perspectives for bond-activation chemistry and catalysis.

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“…[7] Es gibt nur wenige Untersuchungen zu Platin(0)-Komplexen, die zwei NHC-Liganden tragen. [11] Bereits im ersten Beispiel einer Anwendung von NHC-Komplexen in der homogenen Katalyse wurden Palladium(II)-Bis-NHC-Chelatkomplexe untersucht. [8d] Nickel(0)-Bis-NHC-Komplexe sind besser etabliert; sie sind in stçchiometrischen Bindungsaktivierungen und als Katalysatoren in Kreuzkupplungen aktiv.…”

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“…[10] Auf Grundlage des aktuellen Forschungsstandes zu reaktiven d 10 -ML 2 -Systemen erschien es vielversprechend, aktivere Verbindungen durch den Einsatz chelatisierender Bis-NHC-Liganden zu erhalten, die eine cis-Konfiguration am Metallzentrum erzwingen. [11] Bereits im ersten Beispiel einer Anwendung von NHC-Komplexen in der homogenen Katalyse wurden Palladium(II)-Bis-NHC-Chelatkomplexe untersucht. [12a] Inzwischen gibt es Komplexe dieser Liganden für die meisten späten Übergangsmetalle in allen gängigen Oxidationsstufen.…”

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Nickel(0)‐ und Platin(0)‐Bis‐NHC‐Chelatkomplexe

et al. 2014

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d 10 -ML 2 -Fragmente sind seit langem für ihr Potenzial bekannt, unreaktive Bindungen durch oxidative Addition zu aktivieren. Bei der Entwicklung aktiverer Spezies haben sich zwei Ansätze bewährt: Der Einsatz von starken s-Donorliganden, die zu elektronenreichen Metallzentren führen, sowie von Chelatliganden, die eine gewinkelte Koordinationsgeometrie erzeugen. Wir haben beide Strategien kombiniert und Nickel(0)-sowie erstmals Platin(0)-Bis-NHC-Chelatkomplexe synthetisiert. Bis(1,5-Cyclooctadien)nickel(0) und -platin(0) reagieren mit in situ deprotonierten Bisimidazoliumsalzen bei Raumtemperatur zu tetraedrischen oder trigonal-planaren Bis-NHC-Chelat-Olefinkomplexen. Die Synthese und Charakterisierung dieser Komplexe sowie ein erstes Beispiel einer C-C-Bindungsaktivierung mit diesen Systemen werden beschrieben. Wegen der erzwungenen cis-Anordnung zweier NHCs erçffnen diese Verbindungen interessante Perspektiven für Bindungsaktivierungen und Katalyse. Schema 1. Bisphosphanplatin(0)-Systeme, die Bindungsaktivierungen ermçglichen (R = Me, Et; Cy = Cyclohexyl).

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DFT study of the reactivity of methane and dioxygen with d10-L2M complexes

Cited by 11 publications

References 30 publications

DFT Study of the Reaction of a Two-Coordinate Iron(II) Dialkyl Complex with Molecular Oxygen

DFT Study of the Reaction of a Two-Coordinate Iron(II) Dialkyl Complex with Molecular Oxygen

Bis‐NHC Chelate Complexes of Nickel(0) and Platinum(0)

Nickel(0)‐ und Platin(0)‐Bis‐NHC‐Chelatkomplexe

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