Thermochemistry of Oxo Transfer from Coordinated Nitrite in the Dinitro(5,10,15,20-tetrakis(o-pivalamidophenyl)porphinato)iron(III) Anion
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- 作者：Melanie Frangione ; Jennifer Port ; Murtuza Baldiwala ; Andrew Judd ; John Galley ; Magrey DeVega ; Kara Linna ; Leigh Caron ; Elizabeth Anderson ; and John A. Goodwin
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：April 23, 1997
- 年：1997
- 卷：36
- 期：9
- 页码：1904 - 1911
- 全文大小：278K
- 年卷期：v.36,no.9(April 23, 1997)
- ISSN：1520-510X
文摘
The thermochemistry of oxo transfer from coordinated nitrite inthedinitro(5,10,15,20-tetrakis(o-pivalamidophenyl)porphinato)iron(III) anion, ion-paired with thetetrapropylammonium ion,{[FeIIITpivPP(NO2)2]-Pr4N+},has beenevaluated in acetonitrile solution. This oxo-transferhalf-reaction of{[FeIIITpivPP(NO2)2]-Pr4N+}has been assessedon the basis of the determination of the E1/2= +0.54 V vs SHE for the reversible[FeII/IIITpivPP(NO)(NO2)]-/0couple and the measurement of the formation constants for theassociation of NO and NO2- withthemononitroiron(III) porphyrin derivative. The formation constantfor nitric oxide association, KNO, has thevalue(1.21 ± 0.08) × 103. The stability constant,K2, for association of a second nitro ligand in0.0100 Mtetrapropylammonium perchlorate medium has been estimated as 2.18 ×103. The oxo-transfer half-reaction freeenergy, 
G
(X/XO), for additionof oxygen to[FeIITpivPP(NO)(NO2)]-to form{[FeIIITpivPP(NO2)2]-Pr4N+}hasbeen found to be -50 kJ/mol.
G(X/XO), for additionof oxygen to[FeIITpivPP(NO)(NO2)]-to form{[FeIIITpivPP(NO2)2]-Pr4N+}hasbeen found to be -50 kJ/mol.