Participation of Co-Ligands in Electronic Transitions of Platinum(II) Diazabutadiene Complexes

0181550 - UFCH-W 20020182 RIV US eng J - Článek v odborném periodiku
Klein, A. - Slageren van, J. - Záliš, Stanislav
Participation of Co-Ligands in Electronic Transitions of Platinum(II) Diazabutadiene Complexes.
Inorganic Chemistry. Roč. 41, č. 20 (2002), s. 5216-5225. ISSN 0020-1669. E-ISSN 1520-510X
Grant CEP: GA MŠMT ME 439; GA MŠMT OC D14.20
Výzkumný záměr: CEZ:AV0Z4040901
Klíčová slova: molecular photochemical device * resonance Raman-spectra * alpha-diimine ligands
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.950, rok: 2002

The low-lying electronic transitions and photochemical reactions of a series of [(Pr-i-DAB)Pt(R)(2)] (where the co-ligand R = CH3, CD3, adme, neop, neoSi, Cequivalent toC(t)Bu, Cequivalent toCPh, Ph, Mes) compounds were studied using both experimental (electronic absorption and resonance Raman spectroscopy) and theoretical (density functional theory, DFT) techniques. The high-lying filled orbitals were revealed to have a significant co-ligand contribution in the case of alkyl complexes, while this contribution is predominant for the complexes with unsaturated co-ligands. Because the electronic transition removes electron density from the sigma(Pt-C) bond in the former complexes, it is best described as a metal-to-ligand charge transfer transition (MLCT) with partial sigma-bond-to-ligand charge transfer (SBLCT) character. Because the sigma(Pt-C) orbital is not involved in the HOMOs of the latter complexes, the low-lying transitions were characterized.
Trvalý link: http://hdl.handle.net/11104/0001904