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Unusual role of solvents in the syntheses of {Fe-NO}6,7 nitrosyls derived from a ligand with carboxamido nitrogen and thiolato sulfur donors.

Inorganic chemistry (2005-09-27)
Todd C Harrop, Marilyn M Olmstead, Pradip K Mascharak
ABSTRACT

Reaction of excess NO with the S = 3/2 Fe(III) complex (Et4N)2[Fe(PhPepS)(Cl)] (1) in protic solvents such as MeOH affords the {Fe-NO}(7) nitrosyl (Et(4)N)(2)[Fe(PhPepS)(NO)] (2). This distorted square-pyramidal S = 1/2 complex, a product of reductive nitrosylation, is the first example of an {Fe-NO}7 nitrosyl with carboxamido-N and thiolato-S coordination. When the same reaction is performed in aprotic solvents such as MeCN and DMF, the product is a dimeric diamagnetic {Fe-NO}6 complex, (Et4N)2-[{Fe(PhPepS)(NO)}2] (3). Both electrochemical and chemical oxidation of 2 leads to the formation of 3 via a transient five-coordinate {Fe-NO}6 intermediate. The oxidation is NO-centered. The ligand frame is not attacked by excess NO in these reactions.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Iron(III) nitrate nonahydrate, ≥99.95% trace metals basis
Sigma-Aldrich
Iron(III) nitrate nonahydrate, ≥99.999% trace metals basis
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Supelco
Iron standard for AAS, analytical standard, 10.00 g/L Fe in nitric acid, traceable to BAM
Sigma-Aldrich
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