Solvation effects in oxidative addition reaction of Methyliodide to Pt(II) complex: A theoretical study with RISM–SCF method

Hayaki, Seigo; Yokogawa, Daisuke; Sato, Hirofumi; Sakaki, Shigeyoshi

doi:10.1016/j.cplett.2008.04.116

Cited by 35 publications

(21 citation statements)

References 14 publications

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“…In this work, two set of parameters ( "Set A" and "Set B") were examined for the intermolecular interaction. One of them is the same as that in our previous study [12], where nitromethane was used as solvent. The standard Lennard-Jones 12-6 potential plus Coulombic interaction was used and the parameters were determined from the OPLS parameter set [13] and from the set reported by Alper et al [5].…”

Section: Methodsmentioning

confidence: 99%

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A theoretical study of the liquid structure of nitromethane with RISM method

Hayaki

Sato

Sakaki

2009

Journal of Molecular Liquids

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An integral equation theory for molecular liquids, reference interaction site model (RISM), was applied to understand the liquid structure of nitromethane, which is extensively used as a solvent. In the theory, liquid structure is described by a set of pair correlation functions. With the aid of ab initio molecular orbital calculations, representative peaks were able to be related to specific configurations of molecules.

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Section: Methodsmentioning

confidence: 99%

“…RISM has been also combined with ab initio molecular orbital (MO) theory (RISM-SCF) [9][10][11]. It determines the electronic structure of a solute and the solvent distribution around it in a self-consistent manner, successfully applied to various chemical processes in solution phase such as organometallic reaction in solution phase [12].…”

Section: Introductionmentioning

confidence: 99%

A theoretical study of the liquid structure of nitromethane with RISM method

Hayaki

Sato

Sakaki

2009

Journal of Molecular Liquids

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“…Here, we wish to report our recent theoretical work of the oxidative addition of methyliodide (MeI) to PtMe 2 (NH 3 ) 2 ,33 where 2,2′‐bipyridine in the real system was replaced with two NH 3 molecules for brevity. The oxidative addition of MeI to transition metal complexes has also been investigated experimentally34 and theoretically with the PCM method,35 because it is one of important processes in the methanol carbonylation process.…”

Section: Solvation Effects Of Transition Metal Complexesmentioning

confidence: 99%

Theoretical and computational studies of organometallic reactions: successful or not?

Sakaki

Ohnishi

Sato

2010

The Chemical Record

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Theoretical and computational methods are powerful in studying transition metal complexes. Our theoretical studies of C-H σ-bond activation of benzene by Pd(II)-formate complex and that of methane by Ti(IV)-imido complex successfully disclosed that these reactions are understood to undergo heterolytic σ-bond activation and the driving force is the formation of strong O-H and N-H bonds in the former and the latter, respectively. Orbital interactions are considerably different from those of σ-bond activation by oxidative addition. The transmetallation, which is a key process in the cross-coupling reaction, is understood to be heterolytic σ-bond activation. Our theoretical study clarifi ed how to accelerate this transmetallation. Also, we wish to discuss weak points in theoretical and computational studies of large systems including transition metal elements, such as the necessity to incorporate solvation effect and to present quantitatively correct numerical results. The importance of solvation effects is discussed in the oxidative addition of methyliodide to Pt(II) complex which occurs in a way similar to an S N 2 substitution. To apply the CCSD(T) (coupled cluster singles and doubles with perturbative triples correction) method, which is the gold standard of electronic structure theory, to large system, we need to reduce the size of the system by employing a small model. But, such modeling induces neglects of electronic and steric effects of substitutents which are replaced in the small model. Frontier-orbital-consistent quantum-capping potential (FOC-QCP) was recently proposed by our group to incorporate the electronic effects of the substituents neglected in the modeling. The CCSD(T) calculation with the FOC-QCP was successfully applied to large systems including transition metal elements.

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“…The lowest free energy barrier found for complex with n = 2 may be due to greater stability of the five-membered ring transition state TSb, compared to other chelating rings. [6,34]. The relatively large ΔG ‡ value of 88.6 kJ mol −1 , found for the reaction of 1b with MeI in benzene, shows an evidence for the fact that the reaction is slow in very low polar solvents.…”

Section: Free Energy Change Profiles and Bite Angle Effectmentioning

confidence: 86%