Pseudopotential Calculations of Transition Metal Compounds: Scope and Limitations

Frenking, Gernot; Antes, Iris; Böhme, Marlis; Dapprich, Stefan; Ehlers, Andreas W.; Jonas, Volker; Neuhaus, Arndt; Otto, Michael; Stegmann, Ralf; Veldkamp, Achim; Vyboishchikov, Sergei F.

doi:10.1002/9780470125854.ch2

Cited by 207 publications

(85 citation statements)

References 253 publications

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“…Quantum chemical methods have become useful and practical tools in study of TM complexes (14)(15)(16)(17). Particularly, advancements in density functional theory (DFT) (16) and the use of effective core potentials (14,15) have made qualitatively accurate predictions of the structures and chemistry of TM complexes possible at a reasonable computational cost (17).…”

Section: Metal-alkane Binding Energies Have Been Calculated For [Cprementioning

confidence: 99%

“…Particularly, advancements in density functional theory (DFT) (16) and the use of effective core potentials (14,15) have made qualitatively accurate predictions of the structures and chemistry of TM complexes possible at a reasonable computational cost (17). The goals of the present work are twofold: to make computational predictions of the relative stabilities of a selection of alkane -complexes, which will aid synthetic chemists in their efforts toward isolating and fully characterizing such species, and to explain the nature of the alkane-metal interaction in such complexes.…”

Section: Metal-alkane Binding Energies Have Been Calculated For [Cprementioning

confidence: 99%

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Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

Cobar

Khaliullin

Bergman

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

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Metal-alkane binding energies have been calculated for [CpRe(CO) 2](alkane) and [(CO)2M(C5H4)C'C(C5H4)M(CO)2](alkane), where M ‫؍‬ Re or Mn. Calculated binding energies were found to increase with the number of metal-alkane interaction sites. In all cases examined, the manganese-alkane binding energies were predicted to be significantly lower than those for the analogous rhenium-alkane complexes. The metal (Mn or Re)-alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70 -80% of total charge transfer) and from the metal complex to the alkane (20 -30% of the total charge transfer).binding energy ͉ COH activation ͉ DFT calculations ͉ manganese C arbon-hydrogen (COH) bond activation reactions are important from a fundamental point of view, as well as in more practical terms to medicine, academia, and industry, as they are being used for the conversion of common, inexpensive alkanes into reactive (and physiologically active) molecules (1, 2). Many transition metal complexes are now known that can be used to activate COH bonds in alkanes (3). With low-valent metal complexes, the first bond-breaking step involves oxidative addition of an alkane to an unsaturated metal center (Fig. 1). The goal of subsequent steps is to convert the alkyl group R into an alcohol ROH or other potentially useful functionalized organic molecule.Many researchers today are focusing on the development of industrially practical organometallic oxidation catalysts (5-8), but there remain fundamental aspects of the COH activation process that are not fully understood. For instance, it is widely accepted that COH activation reactions proceed via alkane -complex intermediates (3) (Fig. 1, compound 3), and such species have recently been detected and studied in lowtemperature NMR experiments (9-11). Although complexes with intramolecular COH/metal (so-called agostic) interactions have been isolated and crystallographically characterized (3), in systems where strong evidence has been provided for intermolecular metal-alkane coordination in solution (9-11), isolation and solid state structural characterization have not yet been accomplished.† † Intermolecular metal-alkane complexes are therefore one of the most important targets in the study of COH activation; an understanding of the mechanisms of COH activation, which will allow researchers to better control and manipulate the outcome of the reactions, is crucial for the advancement of this area of chemistry.Quantum chemical methods have become useful and practical tools in study of TM complexes (14-17). Particularly, advancements in density functional theory (DFT) (16) and the use of effective core potentials (14, 15) have made qualitatively accurate predictions of the structures and chemistry of TM complexes possible at a reasonable computational cost (17). The goals of the present work are twofold: to make computational predictions of the relative stabilities of a selection of alkane -complexes, which will aid synthetic chemists in th...

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Section: Metal-alkane Binding Energies Have Been Calculated For [Cprementioning

confidence: 99%

Section: Metal-alkane Binding Energies Have Been Calculated For [Cprementioning

confidence: 99%

Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

Cobar

Khaliullin

Bergman

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

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“…Most calculations are therefore done using density functional theory (DFT) often in combination with quasi-relativistic effective core potentials for applications including heavier elements (for an overview see e.g. [10][11][12] ). Regarding molecular geometries and simple reactions, especially Becke's generalized gradient approximation (GGA) exchange functional from 1988 13 together with Perdew's 1986 correlation part 14 (B-P86) has proven as a reliable approach 6,15 in TM chemistry.…”

Section: Introductionmentioning

confidence: 99%

A comparative quantum chemical study of the ruthenium catalyzed olefin metathesis

Piacenza¹,

Hyla‐Kryspin

Grimme

2007

J Comput Chem

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The accurate quantum mechanical description of homogeneous catalysis involving transition-metal complexes is a complicated and computationally demanding task. Hence, in this study the performance of different quantum chemical approaches with respect to the ruthenium catalyzed olefin metathesis of ethylene and RuCl(2)(PH(3))(2)CH(2) as a model system is investigated. All intermediates and transition states that are relevant for the rate determining steps of competing reaction mechanisms (associative and two dissociative pathways) are considered. Results from density functional theory calculations employing B-P86, B97-D, B3-LYP, TPSSh, and B2-PLYP functionals, as well as from MP2 and SCS-MP2 perturbation theory are compared to reference values (relative and reaction energies) obtained at the QCISD(T) level of theory. In particular, the applicability of AO basis sets of increasing size ranging from double-zeta to quadruple-zeta quality is evaluated for representative methods. For some reaction steps, large basis set effects on the order of 10 kcal mol(-1) (50% of Delta E) are observed. Double-zeta type basis sets yield very unreliable results while properly polarized triple-zeta sets provide reaction energies quite close to the basis set limit. The performance of recommended methods is B2-PLYP>TPSSh>B-86 approximately B97-D>SCS-MP2. The often used standard approaches B3-LYP and MP2 provide overall the largest errors. The accurate QCISD(T) computations predict in conclusion (and in agreement with a recent other study) that for the model system considered, the dissociative trans pathway is favored over the dissociative cis pathway and also over the associative reaction mechanism.

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“…|P )(P |Q) −1 (Q| RI-MP2 is known to produce equilibrium geometries that rival density functional theory (DFT) except for transition metal compounds [18]. On the other hand, RI-MP2 is also known to capture long-range correlation effects, which are missing in many popular density functionals.…”

Section: Introductionmentioning

confidence: 99%

Accelerating Resolution-of-the-Identity Second-Order Møller−Plesset Quantum Chemistry Calculations with Graphical Processing Units

et al. 2008

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Pseudopotential Calculations of Transition Metal Compounds: Scope and Limitations

Cited by 207 publications

References 253 publications

Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

A comparative quantum chemical study of the ruthenium catalyzed olefin metathesis

Accelerating Resolution-of-the-Identity Second-Order Møller−Plesset Quantum Chemistry Calculations with Graphical Processing Units

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