Theoretical study of the interaction d¹⁰–s² between Pt(0) and metals on the [Pt(PH₃)₃M] complexes (M = Hg(0), Au(-I))

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• 作者：Fern ; o Mendizabal ; Daniela Donoso ; Claudio Olea-Azar ; Raú ; l Mera
• 关键词：Metallophilic attraction ; Electron correlation effects ; Pseudopotentials
• 刊名：Journal of Molecular Structure ; THEOCHEM
• 出版年：2007
• 期刊代码：63_01661280
• 类别：ch
• 出版时间：18 February 2007
• 卷：803
• 期：1-3
• 页码：39-44
• 文件大小：398 K

摘要

We studied the attraction between [Pt(PH₃)₃] and the metals (Hg(0) and Au(-I)) in the hypothetical [Pt(PH₃)₃M] isoelectronic complexes using ab initio methodology. We found that the changes around the equilibrium distance Pt–M and in the interaction energies are sensitive to the electron correlation potential. This effect was evaluated using several levels of theory, including HF, MPn (n = 2–4), CCSD and CCSD(T). In the [Pt(PH₃)₃Hg] complex, at the different methodology levels are obtained interaction energies at the equilibrium distance R_e (Pt–Hg) range from 10 to 42 kJ/mol. Such magnitude are in the order of a metallophilic interaction. On the other hand, in the [Pt(PH₃)₃Au]⁻ complex, the interaction energies Au–Pt are range from 35 to 129 kJ/mol, beyond the metallophilic interaction. At long-distances, the behaviour of the [Pt(PH₃)₃–M] interaction may be related mainly to electrostatic, charge-induced dipole and dispersion terms, involving the individual properties of [Pt(PH₃)₃] and the individual metals. The dispersion term (R⁻⁶) is found as the principal contribution in the stability at the long and short distances in the [Pt(PH₃)₃Hg] complex. While in [Pt(PH₃)₃Au]⁻ complex, the electrostatic and charge-induced dipole terms are found as the principal contributions in the stability at the long distances.