Vinyl Ruthenium-Modified Biphenyl and 2,2 '-Bipyridines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F15%3A00452688" target="_blank" >RIV/61388955:_____/15:00452688 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/ic503075e" target="_blank" >http://dx.doi.org/10.1021/ic503075e</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/ic503075e" target="_blank" >10.1021/ic503075e</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Vinyl Ruthenium-Modified Biphenyl and 2,2 '-Bipyridines

Popis výsledku v původním jazyce

We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)(3)X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR,and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawingfac-Re(CO)(3)X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared tocomplexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)(3)

Název v anglickém jazyce

Vinyl Ruthenium-Modified Biphenyl and 2,2 '-Bipyridines

Popis výsledku anglicky

We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)(3)X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR,and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawingfac-Re(CO)(3)X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared tocomplexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)(3)

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/LD14129" target="_blank" >LD14129: Struktura a dynamika excitovaných a redoxních stavů fotokatalytických komplexů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2015

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

54

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

16

Strana od-do

3387-3402

Kód UT WoS článku

000352518600040

EID výsledku v databázi Scopus

2-s2.0-84926486662