Bimetallic nickel complexes supported by 2 5 bis phosphine 1 4 hydroquinonate ligands Structural electrochemical and theoretical investigations

Pignotti, Louis R.; Luck, Rudy L.; DELİGÖNÜL, NİHAL; Protasiewicz, John D.; Johnson, Kevin E.; Nguyen, Lillian P.; Urnezius, Eugenijus

doi:10.1016/j.ica.2014.08.049

Bimetallic nickel complexes supported by 2 5 bis phosphine 1 4 hydroquinonate ligands Structural electrochemical and theoretical investigations

Yazarlar (7)

Louis R. Pignotti
Michigan Technological University, Amerika Birleşik Devletleri

Rudy L. Luck
Michigan Technological University, Amerika Birleşik Devletleri

Prof. Dr. Nihal DELİGÖNÜL Tokat Gaziosmanpaşa Üniversitesi, Türkiye

John D. Protasiewicz
Case Western Reserve University, Amerika Birleşik Devletleri

Kevin E. Johnson
Pacific University, Amerika Birleşik Devletleri

Lillian P. Nguyen
University Of Portland, Amerika Birleşik Devletleri

Eugenijus Urnezius
University Of Portland, Amerika Birleşik Devletleri

Makale Türü	Özgün Makale
Makale Alt Türü	SSCI, AHCI, SCI, SCI-Exp dergilerinde yayınlanan tam makale
Dergi Adı	Inorganica Chimica Acta
Dergi ISSN	0020-1693 Wos Dergi Scopus Dergi
Dergi Tarandığı Indeksler	SCI-Expanded
Dergi Grubu	Q4
Makale Dili	İngilizce
Basım Tarihi	01-2015
Cilt No	424
Sayı	1
Sayfalar	274 / 285
DOI Numarası	10.1016/j.ica.2014.08.049
Makale Linki	http://linkinghub.elsevier.com/retrieve/pii/S0020169314005490

Özet

The coordination chemistries of several 2,5-bis(phosphine)-1,4-hydroquinones, (2,5-bis(PiPr2)-3,6-difluoro-1,4-hydroquinone (1a), 2,5-bis(PiPr2)-1,4-hydroquinone (1b), (2,5-bis(PPh2)-3,6-difluoro-1,4-hydroquinone (1c), and 2,5-bis(PPh2)-1,4-hydroquinone (1d)) were investigated. Reactions of these ligands 1a-d with excess (∼2.5) of bis(cyclopentadienide)nickel, and in case of 1a, with bis(pentamethylcyclopentadienide)nickel, resulted in the formation of bimetallic nickel complexes 2a-d and 3a, where both [P,O] chelating pockets of the ligands were occupied by CpNi or Cp^∗Ni moieties, respectively. Cyclic voltammetric (CV) scans on complexes 2a-d contained a common feature of two reversible/quasi-reversible waves and one irreversible redox event. Complex [2a][PF6] was isolated by the oxidation of 2a with ferrocenium hexafluorophosphate. Spectroscopic, structural, and synthetic studies were carried out in order to elucidate the nature of these redox processes. Our results suggest that the reversible and quasi-reversible redox events are ligand-based processes (hydroquinone/semiquinone/quinone), while the irreversible process was assigned as metal-based. These conclusions were supported by additional experimental data and by theoretical calculations. Investigations of chemical reactivity showed that cyclopentadienide ligands in complexes 2a-d can be displaced from the metal centers upon reactions with o-aminothiophenol. One of these derivatives, 4a, containing capping [N,S] o-aminothiophenolate ligands was isolated and fully characterized. A CV scan of complex 4a contained one reversible wave and an irreversible wave at higher potentials. The assignment is complicated by the proton transfer processes accompanying the electron transfer events. Complexes 1a, 2a-c, [2a][PF6] and 4a were characterized by single crystal X-ray diffraction experiments.

Anahtar Kelimeler

Science Direct

BM Sürdürülebilir Kalkınma Amaçları

Atıf Sayıları
WoS	6
SCOPUS	8
Google Scholar	8

Bimetallic nickel complexes supported by 2 5 bis phosphine 1 4 hydroquinonate ligands Structural electrochemical and theoretical investigations

Dergi Adı	INORGANICA CHIMICA ACTA
Yayıncı	Elsevier B.V.
Açık Erişim	Hayır
ISSN	0020-1693
E-ISSN	1873-3255
CiteScore	5,5
SJR	0,393
SNIP	0,638

Bimetallic nickel complexes supported by 2 5 bis phosphine 1 4 hydroquinonate ligands Structural electrochemical and theoretical investigations

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