Nitrogen-15 and Carbon-13 NMR Study of Roussin Salts and Esters and of Pentacyanoferrate Complexes

Anthony R. Butler; Christopher Glidewell; Andrew R. Hyde; Joseph Mcginnis

doi:10.1021/ic00213a012

Nitrogen-15 and Carbon-13 NMR Study of Roussin Salts and Esters and of Pentacyanoferrate Complexes

Anthony R. Butler, Christopher Glidewell, Andrew R. Hyde, Joseph Mcginnis

Research output: Contribution to journal › Article › peer-review

49 Citations (Scopus)

Abstract

High-frequency 15N NMR spectroscopy, using 99% isotopic enrichment for 15N, shows that the Roussin esters Fe2(SR)2(NO)4 (R = Me, i'-Pr) exist as an equimolar mixture of two conformers having and C2v symmetries respectively. Similar 15N spectroscopy of [Fe4X3(NO)7]- (X = S, Se) shows that the solid-state structure for X = S persists in aqueous solution and demonstrates that the anion having X = Se is isostructural in solution; this is confirmed by natural-abundance 77Se NMR. The cubane type Fe4S4(NO)4 retains its structure in solution, and Fe4Se4(NO)4 is isostructural. A combination of 13C and 15N NMR spectra obtained at high frequency with 90% 13C and 99% 15N enrichment reveals two mechanisms for the conversion of [Fe-(CN)5NO]2- to [Fe(CN)5N02]4-, one involving nucleophilic attack by hydroxide and the other attack by nitrite. The spectral data allow ready identification of pentacyanoferrate complexes arising from the reactions of nitroprusside with nucleophiles.

Original language	English
Pages (from-to)	2931-2934
Number of pages	4
Journal	Inorganic Chemistry
Volume	24
Issue number	19
DOIs	https://doi.org/10.1021/ic00213a012
Publication status	Published - 1 Sept 1985

Access to Document

10.1021/ic00213a012

Cite this

@article{c1204223e99e41f3a30b4f4a59b0015e,

title = "Nitrogen-15 and Carbon-13 NMR Study of Roussin Salts and Esters and of Pentacyanoferrate Complexes",

abstract = "High-frequency 15N NMR spectroscopy, using 99% isotopic enrichment for 15N, shows that the Roussin esters Fe2(SR)2(NO)4 (R = Me, i'-Pr) exist as an equimolar mixture of two conformers having and C2v symmetries respectively. Similar 15N spectroscopy of [Fe4X3(NO)7]- (X = S, Se) shows that the solid-state structure for X = S persists in aqueous solution and demonstrates that the anion having X = Se is isostructural in solution; this is confirmed by natural-abundance 77Se NMR. The cubane type Fe4S4(NO)4 retains its structure in solution, and Fe4Se4(NO)4 is isostructural. A combination of 13C and 15N NMR spectra obtained at high frequency with 90% 13C and 99% 15N enrichment reveals two mechanisms for the conversion of [Fe-(CN)5NO]2- to [Fe(CN)5N02]4-, one involving nucleophilic attack by hydroxide and the other attack by nitrite. The spectral data allow ready identification of pentacyanoferrate complexes arising from the reactions of nitroprusside with nucleophiles.",

author = "Butler, {Anthony R.} and Christopher Glidewell and Hyde, {Andrew R.} and Joseph Mcginnis",

year = "1985",

month = sep,

day = "1",

doi = "10.1021/ic00213a012",

language = "English",

volume = "24",

pages = "2931--2934",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Nitrogen-15 and Carbon-13 NMR Study of Roussin Salts and Esters and of Pentacyanoferrate Complexes

AU - Butler, Anthony R.

AU - Glidewell, Christopher

AU - Hyde, Andrew R.

AU - Mcginnis, Joseph

PY - 1985/9/1

Y1 - 1985/9/1

N2 - High-frequency 15N NMR spectroscopy, using 99% isotopic enrichment for 15N, shows that the Roussin esters Fe2(SR)2(NO)4 (R = Me, i'-Pr) exist as an equimolar mixture of two conformers having and C2v symmetries respectively. Similar 15N spectroscopy of [Fe4X3(NO)7]- (X = S, Se) shows that the solid-state structure for X = S persists in aqueous solution and demonstrates that the anion having X = Se is isostructural in solution; this is confirmed by natural-abundance 77Se NMR. The cubane type Fe4S4(NO)4 retains its structure in solution, and Fe4Se4(NO)4 is isostructural. A combination of 13C and 15N NMR spectra obtained at high frequency with 90% 13C and 99% 15N enrichment reveals two mechanisms for the conversion of [Fe-(CN)5NO]2- to [Fe(CN)5N02]4-, one involving nucleophilic attack by hydroxide and the other attack by nitrite. The spectral data allow ready identification of pentacyanoferrate complexes arising from the reactions of nitroprusside with nucleophiles.

AB - High-frequency 15N NMR spectroscopy, using 99% isotopic enrichment for 15N, shows that the Roussin esters Fe2(SR)2(NO)4 (R = Me, i'-Pr) exist as an equimolar mixture of two conformers having and C2v symmetries respectively. Similar 15N spectroscopy of [Fe4X3(NO)7]- (X = S, Se) shows that the solid-state structure for X = S persists in aqueous solution and demonstrates that the anion having X = Se is isostructural in solution; this is confirmed by natural-abundance 77Se NMR. The cubane type Fe4S4(NO)4 retains its structure in solution, and Fe4Se4(NO)4 is isostructural. A combination of 13C and 15N NMR spectra obtained at high frequency with 90% 13C and 99% 15N enrichment reveals two mechanisms for the conversion of [Fe-(CN)5NO]2- to [Fe(CN)5N02]4-, one involving nucleophilic attack by hydroxide and the other attack by nitrite. The spectral data allow ready identification of pentacyanoferrate complexes arising from the reactions of nitroprusside with nucleophiles.

UR - http://www.scopus.com/inward/record.url?scp=33845378629&partnerID=8YFLogxK

U2 - 10.1021/ic00213a012

DO - 10.1021/ic00213a012

M3 - Article

AN - SCOPUS:33845378629

SN - 0020-1669

VL - 24

SP - 2931

EP - 2934

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 19

ER -

Nitrogen-15 and Carbon-13 NMR Study of Roussin Salts and Esters and of Pentacyanoferrate Complexes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this