Spectroscopic Studies and Bonding Model for Nitric Oxide Complexes of Iron Porphyrins

B. B. Wayland; Larry W. Olson

doi:10.1021/ja00826a013

Spectroscopic Studies and Bonding Model for Nitric Oxide Complexes of Iron Porphyrins

B. B. Wayland, Larry W. Olson

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Abstract

Fe^IIITPPCl 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 FenTPP(Cl^-)(NO⁺). In the presence of methanol, Fe^IIITPPCl reacts with excess nitric oxide to produce Fe ^II-TPP(NO). This reaction is thought to proceed via the methanolysis of coordinated NO⁺ in the intermediate Fe^II-TPP(Cl^-)(NO⁺) complex. Fe^IITPP(NO) has a doublet ground state with the odd electron in a molecular orbital with Fe (d,_z2) and NO (σN) character. Fe^IITPP(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 Fe^IITPP(NO) to form FeTPP(NO)₂, which on the basis of magnetic and spectroscopic properties is formulated as Fe^IITPP(NO^-)(NO⁺). Two N-O stretching frequencies are observed consistent with linear Fe^II- NO⁺ and bent Fe^IINO^- units. Bonding models are presented for the nitric oxide complexes and generalized for related complexes of diatomic molecules.

Original language	English (US)
Pages (from-to)	6037-6041
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	96
Issue number	19
DOIs	https://doi.org/10.1021/ja00826a013
State	Published - Sep 1 1974
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Spectroscopic Studies and Bonding Model for Nitric Oxide Complexes of Iron Porphyrins",

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 FenTPP(Cl-)(NO+). In the presence of methanol, FeIIITPPCl reacts with excess nitric oxide to produce Fe II-TPP(NO). This reaction is thought to proceed via the methanolysis of coordinated NO+ in the intermediate FeII-TPP(Cl-)(NO+) complex. FeIITPP(NO) has a doublet ground state with the odd electron in a molecular orbital with Fe (d,z2) 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 FeII- NO+ 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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year = "1974",

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doi = "10.1021/ja00826a013",

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AU - Olson, Larry W.

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N2 - 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 FenTPP(Cl-)(NO+). In the presence of methanol, FeIIITPPCl reacts with excess nitric oxide to produce Fe II-TPP(NO). This reaction is thought to proceed via the methanolysis of coordinated NO+ in the intermediate FeII-TPP(Cl-)(NO+) complex. FeIITPP(NO) has a doublet ground state with the odd electron in a molecular orbital with Fe (d,z2) 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 FeII- NO+ and bent FeIINO- units. Bonding models are presented for the nitric oxide complexes and generalized for related complexes of diatomic molecules.

AB - 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 FenTPP(Cl-)(NO+). In the presence of methanol, FeIIITPPCl reacts with excess nitric oxide to produce Fe II-TPP(NO). This reaction is thought to proceed via the methanolysis of coordinated NO+ in the intermediate FeII-TPP(Cl-)(NO+) complex. FeIITPP(NO) has a doublet ground state with the odd electron in a molecular orbital with Fe (d,z2) 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 FeII- NO+ 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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Spectroscopic Studies and Bonding Model for Nitric Oxide Complexes of Iron Porphyrins

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