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 Anton
PY - 1995/3/1
Y1 - 1995/3/1
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, a = 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, a = 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.
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U2 - 10.1021/ic00109a015
DO - 10.1021/ic00109a015
M3 - Article
AN - SCOPUS:0000644755
SN - 0020-1669
VL - 34
SP - 1090
EP - 1093
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -