Hydrogen-bonding and polar group effects on redox potentials in Mo[HB(Me2pz)3](NO)(SR)2

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

Research output: Contribution to journalArticle

Abstract

A series of Mo thiolate complexes with the formula Mo[HB(Me2Pz)3](NO)(SR)2, R = Et (1), Bun (2), CH2CONHCH3 (3), CH2CON(CH3)2 (4), C2H4CONHCH3 (5), and C2H4CON(CH3)2 (6), have been studied using the methods of cyclic voltammetry, IR and resonance Raman spectroscopy, and for 3 and 5, X-ray crystallography. The polar groups of the thiolate ligands exert an influence on the redox potentials reflected in the E1/2 series for the Mo2+/Mo3+ redox couple recorded in CH3CN: 2, -0.960; 1, -0.940; 5, -0.820; 6, -0.750; 4, -0.740; 3, -0.643 V (relative to SCE). The corresponding frequencies for the ν(NO) band increase in the same order: 2, 1658; 1, 1661; 5, 1663; 6, 1664; 4, 1669; 3, 1671 cm-1, showing a correlation between the redox potential and the nitrosyl frequency. Complex 3 belongs to space group P1 with a = 10.564(4) Å, b= 12.160(5) Å, c = 12.478(6) Å, α = 110.27(3)°, β = 92.64(4)°, γ = 105.96(3)°, V = 1427.8(10) Å3, and Z = 2. Complex 5 belongs to space group P1 with a = 9.565(8) Å, b = 11.480(9) Å, c = 18.510(20) Å, α = 73.35(8)°, β= 77.38(8)°, γ = 88.17(7)°, ν = 1899.2(31) Å3, and Z =2. Complex 3 exhibits a single intraligand N-H⋯S hydrogen bond in the solid state, with even more extensive N-H⋯S bonding evident in solution. By contrast 5 forms an interligand N-H⋯O hydrogen bond which precludes the formation of N-H⋯S hydrogen bonds. Within the series of thiolate complexes examined, simple charge-dipole interactions appear to induce redox potential shifts of several hundred millivolts. The largest shift is observed in 3, which forms intraligand hydrogen bonds. These results underscore the likely importance of charge-dipole interactions involving ligated thiolate sulfur in iron-sulfur redox proteins. From this perspective, hydrogen bonding and its effects on redox potential should be viewed in terms of electrostatic influence exerted on the electronic structure of the redox center.

Original languageEnglish (US)
Pages (from-to)6769-6776
Number of pages8
JournalJournal of the American Chemical Society
Volume116
Issue number15
StatePublished - Jul 27 1994

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Hydrogen Bonding
Oxidation-Reduction
Hydrogen bonds
Hydrogen
Sulfur
Iron-Sulfur Proteins
Raman Spectrum Analysis
X ray crystallography
X Ray Crystallography
Static Electricity
Cyclic voltammetry
Electronic structure
Raman spectroscopy
Electrostatics
Iron
Ligands
Proteins

ASJC Scopus subject areas

  • Chemistry(all)

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Hydrogen-bonding and polar group effects on redox potentials in Mo[HB(Me2pz)3](NO)(SR)2 . / Huang, Jiong; Ostrander, Robert L.; Rheingold, Arnold L.; Leung, Yiuchong; Walters, Marc.

In: Journal of the American Chemical Society, Vol. 116, No. 15, 27.07.1994, p. 6769-6776.

Research output: Contribution to journalArticle

Huang, Jiong ; Ostrander, Robert L. ; Rheingold, Arnold L. ; Leung, Yiuchong ; Walters, Marc. / Hydrogen-bonding and polar group effects on redox potentials in Mo[HB(Me2pz)3](NO)(SR)2 . In: Journal of the American Chemical Society. 1994 ; Vol. 116, No. 15. pp. 6769-6776.
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title = "Hydrogen-bonding and polar group effects on redox potentials in Mo[HB(Me2pz)3](NO)(SR)2",
abstract = "A series of Mo thiolate complexes with the formula Mo[HB(Me2Pz)3](NO)(SR)2, R = Et (1), Bun (2), CH2CONHCH3 (3), CH2CON(CH3)2 (4), C2H4CONHCH3 (5), and C2H4CON(CH3)2 (6), have been studied using the methods of cyclic voltammetry, IR and resonance Raman spectroscopy, and for 3 and 5, X-ray crystallography. The polar groups of the thiolate ligands exert an influence on the redox potentials reflected in the E1/2 series for the Mo2+/Mo3+ redox couple recorded in CH3CN: 2, -0.960; 1, -0.940; 5, -0.820; 6, -0.750; 4, -0.740; 3, -0.643 V (relative to SCE). The corresponding frequencies for the ν(NO) band increase in the same order: 2, 1658; 1, 1661; 5, 1663; 6, 1664; 4, 1669; 3, 1671 cm-1, showing a correlation between the redox potential and the nitrosyl frequency. Complex 3 belongs to space group P1 with a = 10.564(4) {\AA}, b= 12.160(5) {\AA}, c = 12.478(6) {\AA}, α = 110.27(3)°, β = 92.64(4)°, γ = 105.96(3)°, V = 1427.8(10) {\AA}3, and Z = 2. Complex 5 belongs to space group P1 with a = 9.565(8) {\AA}, b = 11.480(9) {\AA}, c = 18.510(20) {\AA}, α = 73.35(8)°, β= 77.38(8)°, γ = 88.17(7)°, ν = 1899.2(31) {\AA}3, and Z =2. Complex 3 exhibits a single intraligand N-H⋯S hydrogen bond in the solid state, with even more extensive N-H⋯S bonding evident in solution. By contrast 5 forms an interligand N-H⋯O hydrogen bond which precludes the formation of N-H⋯S hydrogen bonds. Within the series of thiolate complexes examined, simple charge-dipole interactions appear to induce redox potential shifts of several hundred millivolts. The largest shift is observed in 3, which forms intraligand hydrogen bonds. These results underscore the likely importance of charge-dipole interactions involving ligated thiolate sulfur in iron-sulfur redox proteins. From this perspective, hydrogen bonding and its effects on redox potential should be viewed in terms of electrostatic influence exerted on the electronic structure of the redox center.",
author = "Jiong Huang and Ostrander, {Robert L.} and Rheingold, {Arnold L.} and Yiuchong Leung and Marc Walters",
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T1 - Hydrogen-bonding and polar group effects on redox potentials in Mo[HB(Me2pz)3](NO)(SR)2

AU - Huang, Jiong

AU - Ostrander, Robert L.

AU - Rheingold, Arnold L.

AU - Leung, Yiuchong

AU - Walters, Marc

PY - 1994/7/27

Y1 - 1994/7/27

N2 - A series of Mo thiolate complexes with the formula Mo[HB(Me2Pz)3](NO)(SR)2, R = Et (1), Bun (2), CH2CONHCH3 (3), CH2CON(CH3)2 (4), C2H4CONHCH3 (5), and C2H4CON(CH3)2 (6), have been studied using the methods of cyclic voltammetry, IR and resonance Raman spectroscopy, and for 3 and 5, X-ray crystallography. The polar groups of the thiolate ligands exert an influence on the redox potentials reflected in the E1/2 series for the Mo2+/Mo3+ redox couple recorded in CH3CN: 2, -0.960; 1, -0.940; 5, -0.820; 6, -0.750; 4, -0.740; 3, -0.643 V (relative to SCE). The corresponding frequencies for the ν(NO) band increase in the same order: 2, 1658; 1, 1661; 5, 1663; 6, 1664; 4, 1669; 3, 1671 cm-1, showing a correlation between the redox potential and the nitrosyl frequency. Complex 3 belongs to space group P1 with a = 10.564(4) Å, b= 12.160(5) Å, c = 12.478(6) Å, α = 110.27(3)°, β = 92.64(4)°, γ = 105.96(3)°, V = 1427.8(10) Å3, and Z = 2. Complex 5 belongs to space group P1 with a = 9.565(8) Å, b = 11.480(9) Å, c = 18.510(20) Å, α = 73.35(8)°, β= 77.38(8)°, γ = 88.17(7)°, ν = 1899.2(31) Å3, and Z =2. Complex 3 exhibits a single intraligand N-H⋯S hydrogen bond in the solid state, with even more extensive N-H⋯S bonding evident in solution. By contrast 5 forms an interligand N-H⋯O hydrogen bond which precludes the formation of N-H⋯S hydrogen bonds. Within the series of thiolate complexes examined, simple charge-dipole interactions appear to induce redox potential shifts of several hundred millivolts. The largest shift is observed in 3, which forms intraligand hydrogen bonds. These results underscore the likely importance of charge-dipole interactions involving ligated thiolate sulfur in iron-sulfur redox proteins. From this perspective, hydrogen bonding and its effects on redox potential should be viewed in terms of electrostatic influence exerted on the electronic structure of the redox center.

AB - A series of Mo thiolate complexes with the formula Mo[HB(Me2Pz)3](NO)(SR)2, R = Et (1), Bun (2), CH2CONHCH3 (3), CH2CON(CH3)2 (4), C2H4CONHCH3 (5), and C2H4CON(CH3)2 (6), have been studied using the methods of cyclic voltammetry, IR and resonance Raman spectroscopy, and for 3 and 5, X-ray crystallography. The polar groups of the thiolate ligands exert an influence on the redox potentials reflected in the E1/2 series for the Mo2+/Mo3+ redox couple recorded in CH3CN: 2, -0.960; 1, -0.940; 5, -0.820; 6, -0.750; 4, -0.740; 3, -0.643 V (relative to SCE). The corresponding frequencies for the ν(NO) band increase in the same order: 2, 1658; 1, 1661; 5, 1663; 6, 1664; 4, 1669; 3, 1671 cm-1, showing a correlation between the redox potential and the nitrosyl frequency. Complex 3 belongs to space group P1 with a = 10.564(4) Å, b= 12.160(5) Å, c = 12.478(6) Å, α = 110.27(3)°, β = 92.64(4)°, γ = 105.96(3)°, V = 1427.8(10) Å3, and Z = 2. Complex 5 belongs to space group P1 with a = 9.565(8) Å, b = 11.480(9) Å, c = 18.510(20) Å, α = 73.35(8)°, β= 77.38(8)°, γ = 88.17(7)°, ν = 1899.2(31) Å3, and Z =2. Complex 3 exhibits a single intraligand N-H⋯S hydrogen bond in the solid state, with even more extensive N-H⋯S bonding evident in solution. By contrast 5 forms an interligand N-H⋯O hydrogen bond which precludes the formation of N-H⋯S hydrogen bonds. Within the series of thiolate complexes examined, simple charge-dipole interactions appear to induce redox potential shifts of several hundred millivolts. The largest shift is observed in 3, which forms intraligand hydrogen bonds. These results underscore the likely importance of charge-dipole interactions involving ligated thiolate sulfur in iron-sulfur redox proteins. From this perspective, hydrogen bonding and its effects on redox potential should be viewed in terms of electrostatic influence exerted on the electronic structure of the redox center.

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