Spectroscopic studies and bonding model for nitric oxide complexes of iron porphyrins

B. B. Wayland, Larry Olson

Research output: Contribution to journalArticle

298 Citations (Scopus)

Abstract

FeIIITPPCl reacts reversibly with nitric oxide to form FeTPP(Cl)(NO) which is spectroscopically studied in toluene solution, glass media, and Nujol mulls. This diamagnetic nitric oxide complex is formulated as FeIITPP(Cl-)(NO+). In the presence of methanol, FeIIITPPCl reacts with excess nitric oxide to produce FeIITPP(NO). This reaction is thought to proceed via the methanolysis of coordinated NO+ in the intermediate FeIITPP(Cl-)(NO+) complex. FeIITPP(NO) has a doublet ground state with the odd electron in a molecular orbital with Fe (dz2) and NO (σN) character. FeIITPP(NO) adds nitrogen donors in the sixth coordination position which have epr spectra showing 14N hyperfine from both nitrogen bonded ligands. A second nitric oxide is reversibly coordinated by FeIITPP(NO) to form FeTPP(NO)2, which on the basis of magnetic and spectroscopic properties is formulated as FeIITPP(NO-)(NO+). Two N-O stretching frequencies are observed consistent with linear FeIINO+ and bent FeIINO- units. Bonding models are presented for the nitric oxide complexes and generalized for related complexes of diatomic molecules.

Original languageEnglish (US)
Pages (from-to)6037-6041
Number of pages5
JournalJournal of the American Chemical Society
Volume96
Issue number19
StatePublished - 1974
Externally publishedYes

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Porphyrins
Nitric oxide
Nitric Oxide
Iron
Nitrogen
Toluene
Molecular orbitals
Ground state
Stretching
Glass
Methanol
Ligands
Electrons
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Spectroscopic studies and bonding model for nitric oxide complexes of iron porphyrins. / Wayland, B. B.; Olson, Larry.

In: Journal of the American Chemical Society, Vol. 96, No. 19, 1974, p. 6037-6041.

Research output: Contribution to journalArticle

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abstract = "FeIIITPPCl reacts reversibly with nitric oxide to form FeTPP(Cl)(NO) which is spectroscopically studied in toluene solution, glass media, and Nujol mulls. This diamagnetic nitric oxide complex is formulated as FeIITPP(Cl-)(NO+). In the presence of methanol, FeIIITPPCl reacts with excess nitric oxide to produce FeIITPP(NO). This reaction is thought to proceed via the methanolysis of coordinated NO+ in the intermediate FeIITPP(Cl-)(NO+) complex. FeIITPP(NO) has a doublet ground state with the odd electron in a molecular orbital with Fe (dz2) and NO (σN) character. FeIITPP(NO) adds nitrogen donors in the sixth coordination position which have epr spectra showing 14N hyperfine from both nitrogen bonded ligands. A second nitric oxide is reversibly coordinated by FeIITPP(NO) to form FeTPP(NO)2, which on the basis of magnetic and spectroscopic properties is formulated as FeIITPP(NO-)(NO+). Two N-O stretching frequencies are observed consistent with linear FeIINO+ and bent FeIINO- units. Bonding models are presented for the nitric oxide complexes and generalized for related complexes of diatomic molecules.",
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