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Titolo:
Structure and magnetic properties of trigonal bipyramidal iron nitrosyl complexes
Autore:
Ray, M; Golombek, AP; Hendrich, MP; Yap, GPA; Liable-Sands, LM; Rheingold, AL; Borovik, AS;
Indirizzi:
Carnegie Mellon Univ, Pittsburgh, PA 15213 USA Carnegie Mellon Univ Pittsburgh PA USA 15213 iv, Pittsburgh, PA 15213 USA Univ Kansas, Dept Chem, Lawrence, KS 66045 USA Univ Kansas Lawrence KS USA 66045 nsas, Dept Chem, Lawrence, KS 66045 USA Univ Delaware, Newark, DE 19716 USA Univ Delaware Newark DE USA 19716Univ Delaware, Newark, DE 19716 USA
Titolo Testata:
INORGANIC CHEMISTRY
fascicolo: 13, volume: 38, anno: 1999,
pagine: 3110 - 3115
SICI:
0020-1669(19990628)38:13<3110:SAMPOT>2.0.ZU;2-I
Fonte:
ISI
Lingua:
ENG
Soggetto:
ISOPENICILLIN-N-SYNTHASE; MOLECULAR STEREOCHEMISTRY; ELECTRONIC-STRUCTURE; ACTIVE-SITE; THEORETICAL DESCRIPTION; CRYSTAL-STRUCTURE; NITROSYLMETALLOPORPHYRINS; SUBSTRATE; MODEL; NICKEL(II);
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
38
Recensione:
Indirizzi per estratti:
Indirizzo: Hendrich, MP Carnegie Mellon Univ, Pittsburgh, PA 15213 USA Carnegie Mellon Univ Pittsburgh PA USA 15213 h, PA 15213 USA
Citazione:
M. Ray et al., "Structure and magnetic properties of trigonal bipyramidal iron nitrosyl complexes", INORG CHEM, 38(13), 1999, pp. 3110-3115

Abstract

Non-heme Fe(II) proteins form. stable nitrosyl adducts. However, there arefew synthetic examples of structurally characterized non-heme iron nitrosyl complexes, especially those that are coordinatively unsaturated. Presented herein is a series of non-heme {Fe-NO}(7) complexes with trigonal bipyramidal coordination geometry. These complexes were synthesized with tripodal ligands derived from tris(N-R-carbamoylmethy)amine [1(R)](3-) where R isopropyl (Pr-i), cyclopentyl (cyp), or 3,5-dimethylphenyl (dmp) groups. The R groups of these [1(R)](3-) ligands form cavities around the metal ion that can influence structural and functional properties. The nitrosyl complexes were synthesized by treating the Fe(II) precursors [Fe1(R)](-) with NO at room temperature. These iron nitrosyl complexes have similar molecular structures as determined by X-ray diffraction methods. They differ in their Fe-N-O angles which range from 178.2(5)degrees in [Fe1(i)Pr(NO)](-) to 160.3(2)degrees in [Fe1(dmp)(NO)](-). The observed difference in angle is related tothe cavity size: [Fe1(i)Pr(NO)](-) has the most restricted cavity with a small diameter (similar to 3 Angstrom) while [Fe1(dmp)(NO)](-) is more flexible and larger (similar to 8 Angstrom diameter). This angular difference issupported by EPR measurements which shows that [Fe1(dmp)(NO)](-) has a significantly more rhombic spectrum than that found for [Fe1(i)Pr(NO)](-). Magnetic moment, Mossbauer and EPR data on these {Fe-NO}(7) complexes agree with a electronic configuration of [Fe3+ d(5) HS (S = 5/2)-NO- (S = 1)] that lead to an S = 3/2 ground state via antiferromagnetic coupling.

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Documento generato il 28/09/20 alle ore 17:38:44