TY - JOUR
T1 - An investigation of the chromium oxidation state of a monoanionic chromium tris(catecholate) complex by X-ray absorption and EPR spectroscopies
AU - Pattison, D I
AU - Levina, A
AU - Davies, Michael Jonathan
AU - Lay, P A
PY - 2001/1/15
Y1 - 2001/1/15
N2 - The well-known monoanionic Cr tris(3,5-di-tert-butylcatecholato) complex, [Cr(DTBC)3]-, has been studied by X-ray absorption spectroscopy. The multiple-scattering fit to the XAFS gave good correlation (R = 19.8%) and good values for all of the bond lengths, angles, and Debye-Waller factors. The principal bond lengths and angles around the metal center (Cr-O, 1.96 A; O-C, 1.28 A; O-Cr-O, 81.8 degrees; Cr-O-C, 113.3 degrees) were most consistent with the XRD structure for [Cr(X4C6O2)3]- (X = Cl, Br), compared to those in other oxidation states, [Cr(DTBC)3], [Cr(Cl4C6O2)3], and [Cr(O2C6H4)3]3-. The XANES spectrum shows the main K edge at 6003.3 eV and a preedge peak at 5992.9 eV, which is approximately 8% of the intensity of the main K edge. The XANES data were compared to those for Cr-ehba complexes (ehbaH2 = 2-ethyl-2-hydroxybutanoic acid) of known oxidation states (III, IV, and V) and show, in conjunction with EPR spectroscopy and a reevaluation of XRD structures and theoretical calulations, that the complex is best described as a Cr(V) center with delocalization from the catechol ligands. The [Cr(catecholato)3]n+ (n = 1, 0) complexes have similar EPR spectroscopic and structural properties, respectively, to the 1- complex and are also best described as Cr(V) complexes. Such intermediates are important in the redox reactions of catechol(amine)s, and oxidized amino acids (e.g., DOPA), with carcinogenic Cr(VI) and may have relevance in Cr-induced cancers.
AB - The well-known monoanionic Cr tris(3,5-di-tert-butylcatecholato) complex, [Cr(DTBC)3]-, has been studied by X-ray absorption spectroscopy. The multiple-scattering fit to the XAFS gave good correlation (R = 19.8%) and good values for all of the bond lengths, angles, and Debye-Waller factors. The principal bond lengths and angles around the metal center (Cr-O, 1.96 A; O-C, 1.28 A; O-Cr-O, 81.8 degrees; Cr-O-C, 113.3 degrees) were most consistent with the XRD structure for [Cr(X4C6O2)3]- (X = Cl, Br), compared to those in other oxidation states, [Cr(DTBC)3], [Cr(Cl4C6O2)3], and [Cr(O2C6H4)3]3-. The XANES spectrum shows the main K edge at 6003.3 eV and a preedge peak at 5992.9 eV, which is approximately 8% of the intensity of the main K edge. The XANES data were compared to those for Cr-ehba complexes (ehbaH2 = 2-ethyl-2-hydroxybutanoic acid) of known oxidation states (III, IV, and V) and show, in conjunction with EPR spectroscopy and a reevaluation of XRD structures and theoretical calulations, that the complex is best described as a Cr(V) center with delocalization from the catechol ligands. The [Cr(catecholato)3]n+ (n = 1, 0) complexes have similar EPR spectroscopic and structural properties, respectively, to the 1- complex and are also best described as Cr(V) complexes. Such intermediates are important in the redox reactions of catechol(amine)s, and oxidized amino acids (e.g., DOPA), with carcinogenic Cr(VI) and may have relevance in Cr-induced cancers.
M3 - Journal article
C2 - 11170525
SN - 0020-1669
VL - 40
SP - 214
EP - 217
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -
