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

被引：20
作者：
Harrop, TC
Olmstead, MM
Mascharak, PK [1 ]
机构：
[1] Univ Calif Santa Cruz, Dept Chem & Biochem, Santa Cruz, CA 95064 USA
[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
来源：
INORGANIC CHEMISTRY | 2005年 / 44卷 / 20期
关键词：
D O I：
10.1021/ic050659b
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
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 (Et4N)(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.
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页码：6918 / 6920
页数：3
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共 20 条
[1]   Syntheses, structures, and reactivities of {Fe-NO}6 nitrosyls derived from polypyridine-carboxamide ligands:: Photoactive NO-donors and reagents for S-nitrosylation of alkyl thiols [J].
Afshar, RK ;
Patra, AK ;
Olmstead, MM ;
Mascharak, PK .
INORGANIC CHEMISTRY, 2004, 43 (18) :5736-5743
[2]   Structural and spectroscopic characterization of a five-coordinate {Fe(NO)}6 complex derived from an iron complex with carboxamido N and thiolato S donors [J].
Chatel, S ;
Chauvin, AS ;
Tuchagues, JP ;
Leduc, P ;
Bill, E ;
Chottard, JC ;
Mansuy, D ;
Artaud, I .
INORGANICA CHIMICA ACTA, 2002, 336 :19-28
[3]   Bismercaptoethanediazacyclooctane as a N2S2 chelating agent and Cys-x-Cys mimic for Fe(NO) and Fe(NO)2 [J].
Chiang, CY ;
Miller, ML ;
Reibenspies, JH ;
Darensbourg, MY .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (35) :10867-10874
[4]   An enzyme controlled by light: the molecular mechanism of photoreactivity in nitrile hydratase [J].
Endo, I ;
Odaka, M ;
Yohda, M .
TRENDS IN BIOTECHNOLOGY, 1999, 17 (06) :244-249
[5]   Structural models of the bimetallic subunit at the A-cluster of acetyl coenzyme A synthase/CO dehydrogenase: Binuclear sulfur-bridged Ni-Cu and Ni-Ni complexes and their reactions with CO [J].
Harrop, TC ;
Olmstead, MM ;
Mascharak, PK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (45) :14714-14715
[6]   Fe(III) and Co(III) centers with carboxamido nitrogen and modified sulfur coordination: Lessons learned from nitrile hydratase [J].
Harrop, TC ;
Mascharak, PK .
ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (04) :253-260
[7]   The electronic structures of an isostructural series of octahedral nitrosyliron complexes {Fe-NO}6,7,8 elucidated by Mossbauer spectroscopy [J].
Hauser, C ;
Glaser, T ;
Bill, E ;
Weyhermüller, T ;
Wieghardt, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (18) :4352-4365
[8]   Nitrile hydrolases [J].
Kobayashi, M ;
Shimizu, S .
CURRENT OPINION IN CHEMICAL BIOLOGY, 2000, 4 (01) :95-102
[9]   Synthetic analogues of cysteinate-ligated non-heme iron and non-corrinoid cobalt enzymes [J].
Kovacs, JA .
CHEMICAL REVIEWS, 2004, 104 (02) :825-848
[10]   Structural and functional models of nitrile hydratase [J].
Mascharak, PK .
COORDINATION CHEMISTRY REVIEWS, 2002, 225 (1-2) :201-214
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