Synthesis and electrochemistry of Mo[BH(Me2pz)3](NO)[S(CH2) 2CONH(CH2)2S] as a probe of the effects of N-H⋯-S hydrogen bonding on redox potentials

Jiong Huang, Robert L. Ostrander, Arnold L. Rheingold, Marc Walters

Research output: Contribution to journalArticle

Abstract

A series of bidentate alkanethiolate compounds Mo[BH(Me2pz)3](NO)[SRS], [SRS]2- = [S(CH2)2CONH(CH2)2S]2- (1), [S(CH2)5S]2- (2), and [S(CH2)6S]2- (3), have been synthesized in order to determine the effects of N-H⋯S hydrogen bonding on redox potentials in metal-thiolate complexes. Complex 1 was structurally characterized by X-ray crystallography. It crystallizes in the space group P21/c with a = 11.878(2) Å, b = 10.8040(10) Å, c = 21.453(4) Å, α = 90°, β = 105.54°, γ = 90°, V = 2652.4(7) Å3, Z = 4, and R = 0.0374. Redox potentials of -0.793 V (1), -0.930 V (2), and -1.013 V (3) (relative to SCE) were measured in CH3CN by cyclic voltammetry. A comparison of complexes 1-3 by solution vibrational spectroscopy shows that the high redox potential of 1 may be attributed to the presence of N-H⋯S hydrogen bonds. The nitrosyl stretching frequency, v(NO), was assigned in the resonance Raman spectra of complexes 1-3. This band decreased in frequency in parallel with the decrease in redox potential. For complex 1 in solution the values of the amide N-H stretching frequency, v(NH), 3434 and 3308 cm-1 indicates a hydrogen bonding equilibrium constant of K = [NHbonded]/ [NHfree] = 6.7.

Original languageEnglish (US)
Pages (from-to)1090-1093
Number of pages4
JournalInorganic Chemistry
Volume34
Issue number5
StatePublished - 1995

Fingerprint

Electrochemistry
electrochemistry
Hydrogen bonds
probes
hydrogen
synthesis
Stretching
Vibrational spectroscopy
X ray crystallography
Equilibrium constants
Metal complexes
Amides
amides
Cyclic voltammetry
crystallography
Raman scattering
Raman spectra
hydrogen bonds
Oxidation-Reduction
BH 3

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis and electrochemistry of Mo[BH(Me2pz)3](NO)[S(CH2) 2CONH(CH2)2S] as a probe of the effects of N-H⋯-S hydrogen bonding on redox potentials. / Huang, Jiong; Ostrander, Robert L.; Rheingold, Arnold L.; Walters, Marc.

In: Inorganic Chemistry, Vol. 34, No. 5, 1995, p. 1090-1093.

Research output: Contribution to journalArticle

@article{07379d29a682488cb64e0bbd40536f14,
title = "Synthesis and electrochemistry of Mo[BH(Me2pz)3](NO)[S(CH2) 2CONH(CH2)2S] as a probe of the effects of N-H⋯-S hydrogen bonding on redox potentials",
abstract = "A series of bidentate alkanethiolate compounds Mo[BH(Me2pz)3](NO)[SRS], [SRS]2- = [S(CH2)2CONH(CH2)2S]2- (1), [S(CH2)5S]2- (2), and [S(CH2)6S]2- (3), have been synthesized in order to determine the effects of N-H⋯S hydrogen bonding on redox potentials in metal-thiolate complexes. Complex 1 was structurally characterized by X-ray crystallography. It crystallizes in the space group P21/c with a = 11.878(2) {\AA}, b = 10.8040(10) {\AA}, c = 21.453(4) {\AA}, α = 90°, β = 105.54°, γ = 90°, V = 2652.4(7) {\AA}3, Z = 4, and R = 0.0374. Redox potentials of -0.793 V (1), -0.930 V (2), and -1.013 V (3) (relative to SCE) were measured in CH3CN by cyclic voltammetry. A comparison of complexes 1-3 by solution vibrational spectroscopy shows that the high redox potential of 1 may be attributed to the presence of N-H⋯S hydrogen bonds. The nitrosyl stretching frequency, v(NO), was assigned in the resonance Raman spectra of complexes 1-3. This band decreased in frequency in parallel with the decrease in redox potential. For complex 1 in solution the values of the amide N-H stretching frequency, v(NH), 3434 and 3308 cm-1 indicates a hydrogen bonding equilibrium constant of K = [NHbonded]/ [NHfree] = 6.7.",
author = "Jiong Huang and Ostrander, {Robert L.} and Rheingold, {Arnold L.} and Marc Walters",
year = "1995",
language = "English (US)",
volume = "34",
pages = "1090--1093",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Synthesis and electrochemistry of Mo[BH(Me2pz)3](NO)[S(CH2) 2CONH(CH2)2S] as a probe of the effects of N-H⋯-S hydrogen bonding on redox potentials

AU - Huang, Jiong

AU - Ostrander, Robert L.

AU - Rheingold, Arnold L.

AU - Walters, Marc

PY - 1995

Y1 - 1995

N2 - A series of bidentate alkanethiolate compounds Mo[BH(Me2pz)3](NO)[SRS], [SRS]2- = [S(CH2)2CONH(CH2)2S]2- (1), [S(CH2)5S]2- (2), and [S(CH2)6S]2- (3), have been synthesized in order to determine the effects of N-H⋯S hydrogen bonding on redox potentials in metal-thiolate complexes. Complex 1 was structurally characterized by X-ray crystallography. It crystallizes in the space group P21/c with a = 11.878(2) Å, b = 10.8040(10) Å, c = 21.453(4) Å, α = 90°, β = 105.54°, γ = 90°, V = 2652.4(7) Å3, Z = 4, and R = 0.0374. Redox potentials of -0.793 V (1), -0.930 V (2), and -1.013 V (3) (relative to SCE) were measured in CH3CN by cyclic voltammetry. A comparison of complexes 1-3 by solution vibrational spectroscopy shows that the high redox potential of 1 may be attributed to the presence of N-H⋯S hydrogen bonds. The nitrosyl stretching frequency, v(NO), was assigned in the resonance Raman spectra of complexes 1-3. This band decreased in frequency in parallel with the decrease in redox potential. For complex 1 in solution the values of the amide N-H stretching frequency, v(NH), 3434 and 3308 cm-1 indicates a hydrogen bonding equilibrium constant of K = [NHbonded]/ [NHfree] = 6.7.

AB - A series of bidentate alkanethiolate compounds Mo[BH(Me2pz)3](NO)[SRS], [SRS]2- = [S(CH2)2CONH(CH2)2S]2- (1), [S(CH2)5S]2- (2), and [S(CH2)6S]2- (3), have been synthesized in order to determine the effects of N-H⋯S hydrogen bonding on redox potentials in metal-thiolate complexes. Complex 1 was structurally characterized by X-ray crystallography. It crystallizes in the space group P21/c with a = 11.878(2) Å, b = 10.8040(10) Å, c = 21.453(4) Å, α = 90°, β = 105.54°, γ = 90°, V = 2652.4(7) Å3, Z = 4, and R = 0.0374. Redox potentials of -0.793 V (1), -0.930 V (2), and -1.013 V (3) (relative to SCE) were measured in CH3CN by cyclic voltammetry. A comparison of complexes 1-3 by solution vibrational spectroscopy shows that the high redox potential of 1 may be attributed to the presence of N-H⋯S hydrogen bonds. The nitrosyl stretching frequency, v(NO), was assigned in the resonance Raman spectra of complexes 1-3. This band decreased in frequency in parallel with the decrease in redox potential. For complex 1 in solution the values of the amide N-H stretching frequency, v(NH), 3434 and 3308 cm-1 indicates a hydrogen bonding equilibrium constant of K = [NHbonded]/ [NHfree] = 6.7.

UR - http://www.scopus.com/inward/record.url?scp=0000644755&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000644755&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000644755

VL - 34

SP - 1090

EP - 1093

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -