Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand

Kód výsledku v IS VaVaI

RIV/61388955:_____/21:00532543 - isvavai.cz

Výsledek na webu

http://hdl.handle.net/11104/0311003

DOI - Digital Object Identifier

10.1002/chem.202003636

Jazyk výsledku

angličtina

Název v původním jazyce

Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand

Popis výsledku v původním jazyce

Reaction of [Pt(DMSO)(2)Cl-2] or [Pd(MeCN)(2)Cl-2] with the electron-rich LH=N,N´-bis(4-dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2] (1) but dinuclear [Pd2L4] (2), a paddle-wheel complex. The neutral compounds were characterized through experiments (crystal structures, electrochemistry, UV-vis-NIR spectroscopy, magnetic resonance) and TD-DFT calculations as metal(II) species with noninnocent ligands L-. The reversibly accessible cations [PtL2](+) and [Pd2L4](+) were also studied, the latter as [Pd2L4][B{3,5-(CF3)(2)C6H3}(4)] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [Pt-II(L-)(2)] or [Pt-.(L )(2)], [Pt-II(L0.5-)(2)](+) or [Pt-III(L-)(2)](+), [(Pd-II)(2)(mu-L-)(4)] or [(Pd-1.5)(2)(mu-L0.75-)(4)], and [(Pd-2.5)(2)(mu-L-)(4)](+) or [(Pd-II)(2)(mu-L0.75-)(4)](+). In each case, the first alternative was shown to be most appropriate. Remarkable results include the preference of platinum for mononuclear planar [PtL2] with an N-Pt-N bite angle of 62.8(2)degrees in contrast to [Pd2L4], and the dimetal (Pd-2(4+)-> Pd-2(5+)) instead of ligand (L--> L ) oxidation of the dinuclear palladium compound.

Název v anglickém jazyce

Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand

Popis výsledku anglicky

Reaction of [Pt(DMSO)(2)Cl-2] or [Pd(MeCN)(2)Cl-2] with the electron-rich LH=N,N´-bis(4-dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2] (1) but dinuclear [Pd2L4] (2), a paddle-wheel complex. The neutral compounds were characterized through experiments (crystal structures, electrochemistry, UV-vis-NIR spectroscopy, magnetic resonance) and TD-DFT calculations as metal(II) species with noninnocent ligands L-. The reversibly accessible cations [PtL2](+) and [Pd2L4](+) were also studied, the latter as [Pd2L4][B{3,5-(CF3)(2)C6H3}(4)] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [Pt-II(L-)(2)] or [Pt-.(L )(2)], [Pt-II(L0.5-)(2)](+) or [Pt-III(L-)(2)](+), [(Pd-II)(2)(mu-L-)(4)] or [(Pd-1.5)(2)(mu-L0.75-)(4)], and [(Pd-2.5)(2)(mu-L-)(4)](+) or [(Pd-II)(2)(mu-L0.75-)(4)](+). In each case, the first alternative was shown to be most appropriate. Remarkable results include the preference of platinum for mononuclear planar [PtL2] with an N-Pt-N bite angle of 62.8(2)degrees in contrast to [Pd2L4], and the dimetal (Pd-2(4+)-> Pd-2(5+)) instead of ligand (L--> L ) oxidation of the dinuclear palladium compound.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

27

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

8

Strana od-do

3374-3381

Kód UT WoS článku

000607112000001

EID výsledku v databázi Scopus

2-s2.0-85099294262