Reduced and Superreduced Diplatinum Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F16%3A00458890" target="_blank" >RIV/61388955:_____/16:00458890 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jacs.6b02559" target="_blank" >http://dx.doi.org/10.1021/jacs.6b02559</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.6b02559" target="_blank" >10.1021/jacs.6b02559</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reduced and Superreduced Diplatinum Complexes

Popis výsledku v původním jazyce

A d8–d8 complex [Pt2(μ-P2O5(BF2)4]4– (abbreviated Pt(pop-BF2)4–) undergoes two 1e– reductions at E1/2 = 1.68 and Ep = 2.46 V (vs Fc+/Fc) producing reduced Pt(pop-BF2)5– and superreduced Pt(pop-BF2)6– species, respectively. The EPR spectrum of Pt(pop-BF2)5– and UV–vis spectra of both the reduced and the superreduced complexes, together with TD-DFT calculations, reveal successive filling of the 6pσ orbital accompanied by gradual strengthening of Pt–Pt bonding interactions and, because of 6pσ delocalization, of Pt–P bonds in the course of the two reductions. Mayer–Millikan Pt–Pt bond orders of 0.173, 0.268, and 0.340 were calculated for the parent, reduced, and superreduced complexes, respectively. The second (5–/6) reduction is accompanied by a structural distortion that is experimentally manifested by electrochemical irreversibility. Both reduction steps proceed without changing either d8 Pt electronic configuration, making the superreduced Pt(pop-BF2)6– a very rare 6p2 σ-bonded binuclear complex. However, the Pt–Pt σ bonding interaction is limited by the relatively long bridging-ligand-imposed Pt–Pt distance accompanied by repulsive electronic congestion. Pt(pop-BF2)4– is predicted to be a very strong photooxidant (potentials of +1.57 and +0.86 V are estimated for the singlet and triplet dσ*pσ excited states, respectively).

Název v anglickém jazyce

Reduced and Superreduced Diplatinum Complexes

Popis výsledku anglicky

A d8–d8 complex [Pt2(μ-P2O5(BF2)4]4– (abbreviated Pt(pop-BF2)4–) undergoes two 1e– reductions at E1/2 = 1.68 and Ep = 2.46 V (vs Fc+/Fc) producing reduced Pt(pop-BF2)5– and superreduced Pt(pop-BF2)6– species, respectively. The EPR spectrum of Pt(pop-BF2)5– and UV–vis spectra of both the reduced and the superreduced complexes, together with TD-DFT calculations, reveal successive filling of the 6pσ orbital accompanied by gradual strengthening of Pt–Pt bonding interactions and, because of 6pσ delocalization, of Pt–P bonds in the course of the two reductions. Mayer–Millikan Pt–Pt bond orders of 0.173, 0.268, and 0.340 were calculated for the parent, reduced, and superreduced complexes, respectively. The second (5–/6) reduction is accompanied by a structural distortion that is experimentally manifested by electrochemical irreversibility. Both reduction steps proceed without changing either d8 Pt electronic configuration, making the superreduced Pt(pop-BF2)6– a very rare 6p2 σ-bonded binuclear complex. However, the Pt–Pt σ bonding interaction is limited by the relatively long bridging-ligand-imposed Pt–Pt distance accompanied by repulsive electronic congestion. Pt(pop-BF2)4– is predicted to be a very strong photooxidant (potentials of +1.57 and +0.86 V are estimated for the singlet and triplet dσ*pσ excited states, respectively).

Druh

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

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

138

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

5699-5705

Kód UT WoS článku

000375521100037

EID výsledku v databázi Scopus

2-s2.0-84968919966