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Soluble {[Rh2(μ-OOCCH3)2(dbbpy)2][BF4]}n molecular wire and [Rh2(μ-OOCCH3)2(dbbpy)2L2]2+ complexes; dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine : synthesis and physicochemical characterization.

Autorzy

Magdalena Ćwikowska

Florian P. Pruchnik

Oleksiy Pavlyuk

F. Lafolet

S. Chardon-Noblat

A. Deronzier

Rok wydania

2010

Czasopismo

Polyhedron

Numer woluminu

29

Strony

3059-3065

DOI

10.1016/j.poly.2010.08.003

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Binuclear Rh(II) compounds [Rh2(μ-OOCCH3)2(dbbpy)2(H2O)2](CH3COO)2 (1) (dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine), [Rh2(μ-OOCCH3)2(dbbpy)2(H2O)2](BF4)2·H2O·CH3CN (2), [Rh2(CH3COO)2(C18H24N2)2(CH3CN)2](BF4)2·4CH3CN (3) and {[Rh2(μ-OOCCH3)2(dbbpy)2][BF4]}n (4) have been synthesized and characterized with spectroscopic methods. Structure of complex 3 has been determined using X-ray crystallography. Rhodium atoms in compound 3 have distorted octahedral coordination with O and N atoms in equatorial positions and Rh atom and CH3CN molecule in axial coordination sites. Reduction of rhodium(II) compounds with aqueous 2-propanol leads to the formation of polymetallic compound {[Rh2(μ-OOCCH3)2(dbbpy)2][BF4]}n (4) containing [Rh2]3+ core. Compound 4 shows strong antiferromagnetic properties, μ = 0.18–1.73 M.B. in the range 1.8–300 K, J = −597 cm−1. Electrochemistry of compounds 3 and 4 in CH3CN has been investigated. Compound 4 exhibits a poorly reversible oxidation system at E1/2 = −0.92 V (ΔEp = 0.19 V) and in solution in DMF is slowly oxidized to 3 even in total absence of oxygen. Complex 3 is irreversibly oxidized to Rh(III) compound at Epa = 1.48 V and irreversibly reduced at Epc = −1.02 V to lead to the unstable polynuclear complex 4 in CH3CN.

Słowa kluczowe

Rhodium polynuclear complexes, Molecular wires, Rhodium(II) complexes, Antiferromagnetism, Rhodium(II) electrochemistry, lanthanides, 4′-Di-tert-butyl-2, 2′-bipyridine

Adres publiczny

https://doi.org/10.1016/j.poly.2010.08.003

Strona internetowa wydawcy

http://www.elsevier.com

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