Ligan-to-ligan Charge Transfer States and Photochemical Bond Homolysis in Metal-Carbon Bonded Platinum Complexes.

Kód výsledku v IS VaVaI

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Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Ligan-to-ligan Charge Transfer States and Photochemical Bond Homolysis in Metal-Carbon Bonded Platinum Complexes.

Popis výsledku v původním jazyce

This paper reviews the photochemical Pt-C bond homolysis reactions of metal-carbon bonded platinum compounds. Three types of complexes are considered: [Pt(R)(2)(COD)], [Pt(R)(2)(alpha-diimine)] and [Pt(Me-4)(alpha-diimine)]. This photoreactivity originates in the involvement of the sigma-bonded co-ligands in low-lying excited states. This involvement was proved by time-dependent density-functional theory calculations and resonance Raman spectroscopy. In the case of the platinum(II) complexes, the contribution of the co-ligand to the high-lying filled orbitals increases with increased sigma-donor strength of this ligand. Concurrently, the photoreactivity increases dramatically in the case of the [Pt(R)(2)(COD)] complexes. The corresponding alpha-diimineanalogues are much less reactive due to the smaller co-ligand participation in high-lying filled orbitals. The platinum(IV) complexes [Pt(Me-4)(alpha-diimine)] are very photoreactive, due to the fact that the HOMO has almost exclusively.

Název v anglickém jazyce

Ligan-to-ligan Charge Transfer States and Photochemical Bond Homolysis in Metal-Carbon Bonded Platinum Complexes.

Popis výsledku anglicky

This paper reviews the photochemical Pt-C bond homolysis reactions of metal-carbon bonded platinum compounds. Three types of complexes are considered: [Pt(R)(2)(COD)], [Pt(R)(2)(alpha-diimine)] and [Pt(Me-4)(alpha-diimine)]. This photoreactivity originates in the involvement of the sigma-bonded co-ligands in low-lying excited states. This involvement was proved by time-dependent density-functional theory calculations and resonance Raman spectroscopy. In the case of the platinum(II) complexes, the contribution of the co-ligand to the high-lying filled orbitals increases with increased sigma-donor strength of this ligand. Concurrently, the photoreactivity increases dramatically in the case of the [Pt(R)(2)(COD)] complexes. The corresponding alpha-diimineanalogues are much less reactive due to the smaller co-ligand participation in high-lying filled orbitals. The platinum(IV) complexes [Pt(Me-4)(alpha-diimine)] are very photoreactive, due to the fact that the HOMO has almost exclusively.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2002

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Coordination Chemistry Reviews

ISSN

0010-8545

e-ISSN

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Svazek periodika

230

Číslo periodika v rámci svazku

N/A

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

19

Strana od-do

193-211

Kód UT WoS článku

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EID výsledku v databázi Scopus

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