KOPS - Das Institutionelle Repositorium der Universität Konstanz

How to elucidate and control the redox sequence in vinylbenzoate and vinylpyridine bridged diruthenium complexes

How to elucidate and control the redox sequence in vinylbenzoate and vinylpyridine bridged diruthenium complexes

Zitieren

Dateien zu dieser Ressource

Prüfsumme: MD5:3d87c6c89f02d24f32591858bb3e11da

PEVNY, Florian, Rainer WINTER, Biprajit SARKAR, Stanislav ZÁLIS, 2010. How to elucidate and control the redox sequence in vinylbenzoate and vinylpyridine bridged diruthenium complexes. In: Dalton Transactions. 39(34), pp. 8000-8011. ISSN 1477-9226. eISSN 1477-9234

@article{Pevny2010eluci-13602, title={How to elucidate and control the redox sequence in vinylbenzoate and vinylpyridine bridged diruthenium complexes}, year={2010}, doi={10.1039/c0dt00164c}, number={34}, volume={39}, issn={1477-9226}, journal={Dalton Transactions}, pages={8000--8011}, author={Pevny, Florian and Winter, Rainer and Sarkar, Biprajit and Zális, Stanislav} }

2011-08-31T22:25:05Z 2011-06-09T08:32:18Z How to elucidate and control the redox sequence in vinylbenzoate and vinylpyridine bridged diruthenium complexes Zális, Stanislav deposit-license Zális, Stanislav Vinylbenzoate-bridged diruthenium complexes (RHC[double bond, length as m-dash]CH)(CO)(PiPr3)2Ru(μ-4-OOCC6H4–CH[double bond, length as m-dash]CH)RuCl(CO)(PiPr3)2 (R = Ph, 3a or CF3, 3b) and vinylpyridine-bridged (η6-p-cymene)Cl2Ru(μ-NC5H4-4-CH[double bond, length as m-dash]CH)RuCl(CO)(PiPr3)2 (3c) have been prepared from their monoruthenium precursors and investigated with respect to the sequence of the individual redox steps and electron delocalization in their partially and fully oxidized states. Identification of the primary redox sites rests on the trends in redox potentials and the EPR, IR and Vis/NIR signatures of the oxidized radical cations and is correctly reproduced by quantum chemical investigations. Our results indicate that the trifluoropropenyl complex 3b has an inverse FMO level ordering (Ru1-bridge-Ru2 > terminal vinyl-Ru1 site) when compared to its styryl substituted counterpart 3a such that the primary oxidation site in these systems can be tuned by the choice of the terminal alkenyl ligand. It is further shown that the vinylbenzoate bridge is inferior to the vinylpyridine one with regard to charge and spin delocalization at the radical cation level. According to quantum chemical calculations, the doubly oxidized forms of these complexes have triplet diradical ground states and feature two interconnected oxidized vinyl ruthenium subunits. Pevny, Florian 2010 eng Winter, Rainer Pevny, Florian Winter, Rainer Sarkar, Biprajit Sarkar, Biprajit First publ. in: Dalton Transactions 39 (2010), 34, pp. 8000-8011, DOI: 10.1039/C0DT00164C

Dateiabrufe seit 01.10.2014 (Informationen über die Zugriffsstatistik)

Flo Dalton39.pdf 160

Das Dokument erscheint in:

KOPS Suche


Stöbern

Mein Benutzerkonto