A mixed-valent pentanuclear Cu(II)(4)Cu(I) compound containing a radical-anion ligand.
Inorg Chem
; 48(22): 10643-51, 2009 Nov 16.
Article
en En
| MEDLINE
| ID: mdl-19817402
Reaction of 2,4-(2,2'-dipyridylamino)-6-(2-pyridylhydrazino)-1,3,5-triazine, abbreviated dppht (5), with copper(II) chloride in methanol yields a mixed-valent Cu(II)(4)Cu(I) compound (6), also involving the presence of a radical anion. The single-crystal structure determination for [Cu(5)(5(M))(5(MR))Cl(8)] (6) reveals that the original dppht ligand (5) has been monochlorinated at one of its pyridine rings and oxidized at its hydrazyl moiety, generating the ligand 2,4-(2,2'-dipyridylamino)-6-(2-(5-chloropyridyl)azo)-1,3,5-triazine (5(M)). Moreover, the molecular structure of 6 indicates that one of the two coordinated ligands 5(M) is in a radical-anion state, symbolized as 5(MR), characterized by a typical N-N bond length of about 1.33 A for a one-electron reduced azo group. The nature of this unique [Cu(II)(4)Cu(I)(radical)] assembly is corroborated by X-ray absorption spectroscopy, electron paramagnetic resonance, and magnetic susceptibility measurements. Density-functional theory calculations are consistent with the unprecedented structural features and support the spectroscopic data.
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Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Cobre
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En
Revista:
Inorg Chem
Año:
2009
Tipo del documento:
Article
País de afiliación:
Países Bajos
Pais de publicación:
Estados Unidos