Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB).

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030214" target="_blank" >RIV/61388955:_____/03:54030214 - isvavai.cz</a>

Výsledek na webu

—

DOI - Digital Object Identifier

—

Jazyk výsledku

angličtina

Název v původním jazyce

Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB).

Popis výsledku v původním jazyce

The reactions of [fac-Re(CO)3(bpy)(MeOH)](PF6) with the TCNX ligands (TCNE, TCNQ, TCNB) in CH2Cl2 gave very different results. No reaction was observed with TCNB (1,2,4,5-tetracyanobenzene) whereas TCNE produced very labile intermediates which convertedunder mild conditions to structurally characterized {(&#61549;-CN)[fac-Re(CO)3(bpy)]2}(PF6) with an eclipsed conformation relative to the Re-CN-Re axis. With TCNQ a stable tetranuclear complex {(&#61549;4-TCNQ)[Re(CO)3(bpy)]4}(BF4)4 was obtained. Its structural, electrochemical and spectroscopic analysis indicates only negligible charge transfer from the rhenium(I) centers to the extremely strong &#61552; acceptor TCNQ. DFT calculations were used to confirm and explain the absence of electron delocalization from the metals to the TCNQ bridge. Correspondingly, the X-band and high-frequency (285 GHz) EPR data well as the IR and UV/VIS/NIR spectroelectrochemical results support the almost total confinement of the added electron.

Název v anglickém jazyce

Proof of Innocence for the Quintessential Noninnocent Ligand TCNQ in its Tetranuclear Complex with Four [fac-Re(CO)3(bpy)]+ Groups: Unusually Different Reactivity of the TCNX Ligands (TCNX = TCNE, TCNQ, TCNB).

Popis výsledku anglicky

The reactions of [fac-Re(CO)3(bpy)(MeOH)](PF6) with the TCNX ligands (TCNE, TCNQ, TCNB) in CH2Cl2 gave very different results. No reaction was observed with TCNB (1,2,4,5-tetracyanobenzene) whereas TCNE produced very labile intermediates which convertedunder mild conditions to structurally characterized {(&#61549;-CN)[fac-Re(CO)3(bpy)]2}(PF6) with an eclipsed conformation relative to the Re-CN-Re axis. With TCNQ a stable tetranuclear complex {(&#61549;4-TCNQ)[Re(CO)3(bpy)]4}(BF4)4 was obtained. Its structural, electrochemical and spectroscopic analysis indicates only negligible charge transfer from the rhenium(I) centers to the extremely strong &#61552; acceptor TCNQ. DFT calculations were used to confirm and explain the absence of electron delocalization from the metals to the TCNQ bridge. Correspondingly, the X-band and high-frequency (285 GHz) EPR data well as the IR and UV/VIS/NIR spectroelectrochemical results support the almost total confinement of the added electron.

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

—

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

2003

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

42

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

7018-7025

Kód UT WoS článku

—

EID výsledku v databázi Scopus

—