Thermochemistry of oxo transfer from coordinated nitrite in the dinitro(5,10,15,20-tetrakis(o-pivalamidophenyl)porphinato)iron(III) anion

被引：16

作者：

Frangione, M ^{[1
]}

Port, J ^{[1
]}

Baldiwala, M ^{[1
]}

Judd, A ^{[1
]}

Galley, J ^{[1
]}

DeVega, M ^{[1
]}

Linna, K ^{[1
]}

Caron, L ^{[1
]}

Anderson, E ^{[1
]}

Goodwin, JA ^{[1
]}

机构：

[1] ECKERD COLL,COLLEGIUM NAT SCI,ST PETERSBURG,FL 33733

来源：

INORGANIC CHEMISTRY | 1997年 / 36卷 / 09期

关键词：

D O I：

10.1021/ic9608915

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The thermochemistry of oxo transfer from coordinated nitrite in the dinitro(5,10,15,20-tetrakis(o-pivalamidophenyl)-porphinato)iron(III) anion, ion-paired with the tetrapropylammonium ion, {[Fe(III)TpivPP(NO2)(2)]-Pr4N+}, has been evaluated in acetonitrile solution. This ore-transfer half-reaction of {[Fe(III)TpivPP(NO2)(2)]-Pr4N+} has been assessed on the basis of the determination of the E-1/2 = +0.54 V vs SHE for the reversible [Fe(II/III)TpivPP(NO)(NO2)]-(/0) couple and the measurement of the formation constants for the association of NO and NO2- with the mononitroiron(III) porphyrin derivative. The formation constant for nitric oxide association, K-NO, has the value (1.21 +/- 0.08) x 10(3). The stability constant, K-2, for association of a second nitro ligand in 0.0100 M tetrapropylammonium perchlorate medium has been estimated as 2.18 x 10(3)., The oxo-transfer half-reaction free energy, Delta G((X/XO))degrees for addition of oxygen to [Fe(II)TpivPP(NO)(NO2)](-) to form {[Fe(III)TpivPP(NO2)(2)]-Pr4N+} has been found to be -50 kJ/mol.

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页码：1904 / 1911

页数：8

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