Chapter Two - Three Redox States of Metallonitrosyls in Aqueous Solution
ADVANCES IN INORGANIC CHEMISTRY, VOL 67: NO RELATED CHEMISTRY(2015)
摘要
This contribution deals with the structure and reactivity of bound nitrosyl in transition metal centers (group 8:Fe, Ru,Os).The focus is set on pseudooctahedral nitrosyl-complexes with coordination number 5 and 6, containing ancillary coligands of both heme- and non-heme type. The discussion is organized in terms of Enemark and Feltham's classification, selecting complexes within the {MNO}" framework (n=6, 7, and 8). The examples have been chosen for a best description of the electronic structures in terms of modern structural, spectroscopica I, and computational methodologies. The selected {MNO}(6,7,8) species reflect the occurrence of three redox states of bound nitrosyl, frequently (though not always) described as NOH, NO, and NO for n=6, 7, and 8, respectively. The analysis is centered on the members of a series of complexes for which the three redox states have been observed on the same platform, viz., [Fe(CN)(5)(NO)](2,3,4) and [Ru(Me-3[9]aneN(3))(bpy) (NO)](3,2,1+) in aqueous solutions. The influence of the donor acceptor character of the coligands is specifically addressed with emphasis on the ligand trans-to nitrosyl, showing that the latter group may exert a delabilizing influence (as NO), as well as a labilizing one (NO NO) on the trans-liga nd. On the other hand, typical electrophilic reactivity patterns (toward different n ucleophi les) are analyzed for M NOH and nucleophilic reactivity (with 02) is described for the reduced species, M NO and M (NOH). In the latter case, protonation is described by characterizing the bound HNO species. Important differences are highlighted in the chemistry of bound NO and HNO, revealing the strong and mild reluctant abilities of these species, respectively. The chemistry is analyzed in terms of the biological relevance to the behavior of nitrite- and NO -red uctases and other NO-related enzymes.
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