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Titolo:
Copper(II) complexes with unusual axial phenolate coordination as structural models for the active site in galactose oxidase: X-ray crystal structures and spectral and redox properties of [Cu(bpnp)X] complexes
Autore:
Vaidyanathan, M; Viswanathan, R; Palaniandavar, M; Balasubramanian, T; Prabhaharan, P; Muthiah, TP;
Indirizzi:
Bharathidasan Univ, Dept Chem, Tiruchchirappalli 620024, India Bharathidasan Univ Tiruchchirappalli India 620024 rappalli 620024, India
Titolo Testata:
INORGANIC CHEMISTRY
fascicolo: 25, volume: 37, anno: 1998,
pagine: 6418 - 6427
SICI:
0020-1669(199812)37:25<6418:CCWUAP>2.0.ZU;2-6
Fonte:
ISI
Lingua:
ENG
Soggetto:
SPIN-RESONANCE SPECTRA; ELECTRONIC-PROPERTIES; IRON(III) COMPLEXES; IMIDAZOLE LIGANDS; O,N LIGANDS; CHEMISTRY;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
41
Recensione:
Indirizzi per estratti:
Indirizzo: Palaniandavar, M Bharathidasan Univ, Dept Chem, Tiruchchirappalli 620024, India Bharathidasan Univ Tiruchchirappalli India 620024 India
Citazione:
M. Vaidyanathan et al., "Copper(II) complexes with unusual axial phenolate coordination as structural models for the active site in galactose oxidase: X-ray crystal structures and spectral and redox properties of [Cu(bpnp)X] complexes", INORG CHEM, 37(25), 1998, pp. 6418-6427

Abstract

The crystal structures of [Cu(bpnp)(SCN)]. NH4SCN (1), [Cu(bpnp)(CH3COO)]. CH3OH . C8H10 (2), and [Cu-(bpnp)ClO4] (3) [Hbpnp = 2-(bis(pyrid-2-ylmethyl) aminomethyl)-4-nitrophenol] reveal a distorted square pyramidal geometryaround Cu(II) with an unusual axial coordination of phenolate. The mononuclear complex [Cu(bpnp)(SCN)]. NH4SCN crystallizes in the triclinic space group P (1) over bar with a = 10.796(2) Angstrom, b = 10.804(2) Angstrom, 12.559(2) Angstrom, alpha = 71.38(1)degrees, beta = 72.68(1)degrees, gamma = 61.69(1)degrees, and Z = 2. The mononuclear acetate [Cu(bpnp)(CH3COO)]. CH3OH . C8H10 crystallizes in the triclinic space group P (1) over bar with a =10.480(6) Angstrom, b = 12.116(4) Angstrom, c = 12.547(3) Angstrom, alpha = 98.77(3)degrees, beta = 113.37(3)degrees, gamma = 100.78(3)degrees, and Z= 2. The binuclear perchlorate complex crystallizes in the monoclinic space group C2/c with a 13.417(3) Angstrom, b = 20.095(2) Angstrom, c = 16.401(2) Angstrom, alpha = 102.21(2)degrees, and Z = 8. The coordination plane inall these complexes is comprised of the tertiary amine and two pyridine nitrogens. The fourth equatorial position is occupied by SCN-/CH3COO- in the mononuclear complexes but by the coordinated phenolate ion from the adjacent molecule in the perchlorate complex, resulting in its dimerization. The unusual occupation of phenolate ion in the axial site is possibly due to thesteric constraint at copper imposed by the 5,5,6-chelate ring sequence. The thiocyanate/acetate coordination geometry is reminiscent of the active site of the radical copper enzyme galactose oxidase (GOase) with an axial phenolate and equatorial SCN-/CH3COO- ligands. Further, the present complexes exhibit several spectral features also similar to this enzyme. The additionof chloride or thiocyanate or acetate ions dissociates the dimeric structure of the perchlorate complex to produce the corresponding monomeric derivatives. The study of the interaction of the acetate complex with N-3(-) and CN- ions provide insight into the anion binding properties of the enzyme. The sensitivity of the acetate complex to protons suggests the facile dissociation of the axial phenolate which then acts as a base to bind to protons., The implication of this reaction to the GOase mechanism is discussed.

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Documento generato il 04/12/20 alle ore 19:55:14