IR Spectroelectrochemical Investigation of the Disproportionation of W2(SBz)2(CO)8−

Michael G. Hill; Xi Hai Mu; Laurence D. Rosenhein; Kent R. Mann; Franklin A. Schultz

doi:10.1021/ic00046a022

IR Spectroelectrochemical Investigation of the Disproportionation of W₂(SBz)₂(CO)₈⁻

Michael G. Hill, Xi Hai Mu, Laurence D. Rosenhein, Kent R. Mann, Franklin A. Schultz

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Abstract

The UV-vis and IR spectroelectrochemistry of W₂(SBz)₂(CO)₈^2- (1) in 0.1 M (TBA)PF₆/CH₂C1₂ is reported (where SB_z⁻ = benzyl mercaptide). The reversible 2e⁻ oxidation of W₂(SBz)₂(CO)₈^2- is analyzed in terms of the individual le^_ redox potentials, E°'_-/2- and E°'_O- by measuring the homogeneous disproportionation constant, K_disp, of the electrochemically generated W₂(SBz)₂(CO)₈~ radical. At 25 °C, we find Adisp equal to 7500 ± 4000. This value places E°'_-/2- at a potential nearly 0.23 V positive of E°'_0/- (E°'_-/2- = -0.46 V; E°'_0/- = 0.69 V vs aqueous AgCl/Ag). The reversal in positions of the le⁻ redox potentials drives the disproportionation reaction and is rationalized to be a consequence of the electronic destabilization of W₂(SBz)₂(CO)₈~ relative to W₂(SBz)₂(CO)₈^2- and W₂(SBz)₂(CO)₈.

Original language	English (US)
Pages (from-to)	4108-4111
Number of pages	4
Journal	Inorganic chemistry
Volume	31
Issue number	20
DOIs	https://doi.org/10.1021/ic00046a022
State	Published - 1992
Externally published	Yes

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@article{84c79793a5f94c7ea2b4bb1aacf855da,

title = "IR Spectroelectrochemical Investigation of the Disproportionation of W2(SBz)2(CO)8−",

abstract = "The UV-vis and IR spectroelectrochemistry of W2(SBz)2(CO)82- (1) in 0.1 M (TBA)PF6/CH2C12 is reported (where SBz− = benzyl mercaptide). The reversible 2e− oxidation of W2(SBz)2(CO)82- is analyzed in terms of the individual le_ redox potentials, E°'-/2- and E°'O- by measuring the homogeneous disproportionation constant, Kdisp, of the electrochemically generated W2(SBz)2(CO)8~ radical. At 25 °C, we find Adisp equal to 7500 ± 4000. This value places E°'-/2- at a potential nearly 0.23 V positive of E°'0/- (E°'-/2- = -0.46 V; E°'0/- = 0.69 V vs aqueous AgCl/Ag). The reversal in positions of the le− redox potentials drives the disproportionation reaction and is rationalized to be a consequence of the electronic destabilization of W2(SBz)2(CO)8~ relative to W2(SBz)2(CO)82- and W2(SBz)2(CO)8.",

author = "Hill, {Michael G.} and Mu, {Xi Hai} and Rosenhein, {Laurence D.} and Mann, {Kent R.} and Schultz, {Franklin A.}",

year = "1992",

doi = "10.1021/ic00046a022",

language = "English (US)",

volume = "31",

pages = "4108--4111",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - IR Spectroelectrochemical Investigation of the Disproportionation of W2(SBz)2(CO)8−

AU - Hill, Michael G.

AU - Mu, Xi Hai

AU - Rosenhein, Laurence D.

AU - Mann, Kent R.

AU - Schultz, Franklin A.

PY - 1992

Y1 - 1992

N2 - The UV-vis and IR spectroelectrochemistry of W2(SBz)2(CO)82- (1) in 0.1 M (TBA)PF6/CH2C12 is reported (where SBz− = benzyl mercaptide). The reversible 2e− oxidation of W2(SBz)2(CO)82- is analyzed in terms of the individual le_ redox potentials, E°'-/2- and E°'O- by measuring the homogeneous disproportionation constant, Kdisp, of the electrochemically generated W2(SBz)2(CO)8~ radical. At 25 °C, we find Adisp equal to 7500 ± 4000. This value places E°'-/2- at a potential nearly 0.23 V positive of E°'0/- (E°'-/2- = -0.46 V; E°'0/- = 0.69 V vs aqueous AgCl/Ag). The reversal in positions of the le− redox potentials drives the disproportionation reaction and is rationalized to be a consequence of the electronic destabilization of W2(SBz)2(CO)8~ relative to W2(SBz)2(CO)82- and W2(SBz)2(CO)8.

AB - The UV-vis and IR spectroelectrochemistry of W2(SBz)2(CO)82- (1) in 0.1 M (TBA)PF6/CH2C12 is reported (where SBz− = benzyl mercaptide). The reversible 2e− oxidation of W2(SBz)2(CO)82- is analyzed in terms of the individual le_ redox potentials, E°'-/2- and E°'O- by measuring the homogeneous disproportionation constant, Kdisp, of the electrochemically generated W2(SBz)2(CO)8~ radical. At 25 °C, we find Adisp equal to 7500 ± 4000. This value places E°'-/2- at a potential nearly 0.23 V positive of E°'0/- (E°'-/2- = -0.46 V; E°'0/- = 0.69 V vs aqueous AgCl/Ag). The reversal in positions of the le− redox potentials drives the disproportionation reaction and is rationalized to be a consequence of the electronic destabilization of W2(SBz)2(CO)8~ relative to W2(SBz)2(CO)82- and W2(SBz)2(CO)8.

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DO - 10.1021/ic00046a022

M3 - Article

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -

IR Spectroelectrochemical Investigation of the Disproportionation of W₂(SBz)₂(CO)₈⁻

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