About: (alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	The electrochemical behaviour of the complexes [Re(CO)(3)X(alpha-diimine)], X = Cl or Br, alpha-diimine = 1,4-di-tert-butyl-1,4-diaza-1,3-diene, was reinvestigated using cyclic voltammetry accompanied by IR and UV-vis spectroelectrochemistry. While the reduction results in the loss of halide, as necessary for the electrocatalytic activity of related diimine compounds, a reversible oxidation could be observed for the chloro complex 1 (X = Cl). The conversion of 1 to 1(+) in CH2Cl2 or CH3CN is accompanied by high-frequency shifts (Delta v = 73-114 cm (1)) of the three carbonyl stretching bands, by a considerable change in carbonyl stretching modes, and by changed absorption in the visible region. DFT calculations support the spectroelectrochemical results and suggest an unusually large g anisotropy (g(1) 1.38, g(2) 2.06, g(3) 3.20) which explains the absence of detectable EPR signals for 1(+) under normal X band conditions. Frontier orbitals calculated by DFT for 1 reveal two close lying occupied orbitals (HOMO, HOMO-1) with Re-Cl character and a diimine based LUMO. The electrochemical behaviour of the complexes [Re(CO)(3)X(alpha-diimine)], X = Cl or Br, alpha-diimine = 1,4-di-tert-butyl-1,4-diaza-1,3-diene, was reinvestigated using cyclic voltammetry accompanied by IR and UV-vis spectroelectrochemistry. While the reduction results in the loss of halide, as necessary for the electrocatalytic activity of related diimine compounds, a reversible oxidation could be observed for the chloro complex 1 (X = Cl). The conversion of 1 to 1(+) in CH2Cl2 or CH3CN is accompanied by high-frequency shifts (Delta v = 73-114 cm (1)) of the three carbonyl stretching bands, by a considerable change in carbonyl stretching modes, and by changed absorption in the visible region. DFT calculations support the spectroelectrochemical results and suggest an unusually large g anisotropy (g(1) 1.38, g(2) 2.06, g(3) 3.20) which explains the absence of detectable EPR signals for 1(+) under normal X band conditions. Frontier orbitals calculated by DFT for 1 reveal two close lying occupied orbitals (HOMO, HOMO-1) with Re-Cl character and a diimine based LUMO. (en)
Title	(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side (alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side (en)
skos:prefLabel	(alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side (alpha-Diimine)tricarbonylhalorhenium complexes: the oxidation side (en)
skos:notation	RIV/61388955:_____/12:00375976!RIV13-AV0-61388955
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(LD11086), P(ME10124), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika	3
http://linked.open...vai/riv/dodaniDat	2013
http://linked.open...aciTvurceVysledku	Fiedler, Jan Záliš, Stanislav
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	121736
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/12:00375976
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	(alpha-Diimine)tricarbonylhalorhenium complexes; electrochemistry; metal carbonyl complexes (en)
http://linked.open.../riv/klicoveSlovo	(alpha-Diimine)tricarbonylhalorhenium complexes metal carbonyl complexes electrochemistry
http://linked.open...odStatuVydavatele	GB - Spojené království Velké Británie a Severního Irska
http://linked.open...ontrolniKodProRIV	[052E4A0E996C]
http://linked.open...i/riv/nazevZdroje	Dalton Transactions
http://linked.open...in/vavai/riv/obor	CG
http://linked.open...ichTvurcuVysledku	2 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	Quantum chemical interpretation and prediction of spectral characteristics of heavy transition metal complexes Photoinduced Charge Separation in Metalloprotein-Based Systems: Theory and Experiment
http://linked.open...UplatneniVysledku	2012
http://linked.open...v/svazekPeriodika	41
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Kaim, W. Záliš, Stanislav Bubrin, M. Drozdz, A.
http://linked.open...ain/vavai/riv/wos	000298753800041
http://linked.open...n/vavai/riv/zamer	Struktura, reaktivita a dynamika molekulárních a biomolekulárních systémů: teorie, experiment, aplikace
issn	1477-9226
number of pages	7 (xsd:int)
http://bibframe.org/vocab/doi	10.1039/c1dt11449b

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