Direct Determination of the Self-Exchange Rate of a Nickel(IV/III) Bis(oxime-imine) Complex. Investigation of Orientation Effects in Electron-Transfer Reactions

Rosemary A. Marusak; Christopher Sharp; A. Graham Lappin

doi:10.1021/ic00347a024

Direct Determination of the Self-Exchange Rate of a Nickel(IV/III) Bis(oxime-imine) Complex. Investigation of Orientation Effects in Electron-Transfer Reactions

Rosemary A. Marusak, Christopher Sharp, A. Graham Lappin

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Abstract

The electron self-exchange rate for the couple [Ni^IV/^IIIMe₂L(l)]^2+/+(Me₂L(1)H₂= 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13-diene-2,15-dione dioxime) has been determined as 2.4 × 10⁴ M⁻¹s⁻¹at 25 °C and 0.10 M ionic strength by ¹H NMR line broadening. Rate constants for cross-reactions calculated with use of this self-exchange rate in the Marcus relationship show good agreement with measured values. The effect of the paramagnetic ions [Cr(edta)]−, [Niⁱⁱⁱ, Me₂L(1)]⁺, and [Cr(phen)₃]³⁺on the ’H NMR relaxation rates of the cobalt(III) complex [Co^mMe₂L(1)]⁺ has been used to investigate ion-pair structure in solution. These ion pairs serve as models for the electron-transfer precursor assemblies in the self-exchange reaction and two cross-reactions, respectively. Marcus calculations are relatively insensitive to the precursor structures. However, these structures provide a basis for interpretation of stereoselectivity data.

Original language	English (US)
Pages (from-to)	4453-4456
Number of pages	4
Journal	Inorganic chemistry
Volume	29
Issue number	22
DOIs	https://doi.org/10.1021/ic00347a024
State	Published - 1990
Externally published	Yes

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title = "Direct Determination of the Self-Exchange Rate of a Nickel(IV/III) Bis(oxime-imine) Complex. Investigation of Orientation Effects in Electron-Transfer Reactions",

abstract = "The electron self-exchange rate for the couple [NiIV/IIIMe2L(l)]2+/+(Me2L(1)H2= 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13-diene-2,15-dione dioxime) has been determined as 2.4 × 104 M−1s−1at 25 °C and 0.10 M ionic strength by 1H NMR line broadening. Rate constants for cross-reactions calculated with use of this self-exchange rate in the Marcus relationship show good agreement with measured values. The effect of the paramagnetic ions [Cr(edta)]−, [Niiii, Me2L(1)]+, and [Cr(phen)3]3+on the {\textquoteright}H NMR relaxation rates of the cobalt(III) complex [ComMe2L(1)]+ has been used to investigate ion-pair structure in solution. These ion pairs serve as models for the electron-transfer precursor assemblies in the self-exchange reaction and two cross-reactions, respectively. Marcus calculations are relatively insensitive to the precursor structures. However, these structures provide a basis for interpretation of stereoselectivity data.",

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year = "1990",

doi = "10.1021/ic00347a024",

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T1 - Direct Determination of the Self-Exchange Rate of a Nickel(IV/III) Bis(oxime-imine) Complex. Investigation of Orientation Effects in Electron-Transfer Reactions

AU - Marusak, Rosemary A.

AU - Sharp, Christopher

AU - Lappin, A. Graham

PY - 1990

Y1 - 1990

N2 - The electron self-exchange rate for the couple [NiIV/IIIMe2L(l)]2+/+(Me2L(1)H2= 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13-diene-2,15-dione dioxime) has been determined as 2.4 × 104 M−1s−1at 25 °C and 0.10 M ionic strength by 1H NMR line broadening. Rate constants for cross-reactions calculated with use of this self-exchange rate in the Marcus relationship show good agreement with measured values. The effect of the paramagnetic ions [Cr(edta)]−, [Niiii, Me2L(1)]+, and [Cr(phen)3]3+on the ’H NMR relaxation rates of the cobalt(III) complex [ComMe2L(1)]+ has been used to investigate ion-pair structure in solution. These ion pairs serve as models for the electron-transfer precursor assemblies in the self-exchange reaction and two cross-reactions, respectively. Marcus calculations are relatively insensitive to the precursor structures. However, these structures provide a basis for interpretation of stereoselectivity data.

AB - The electron self-exchange rate for the couple [NiIV/IIIMe2L(l)]2+/+(Me2L(1)H2= 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13-diene-2,15-dione dioxime) has been determined as 2.4 × 104 M−1s−1at 25 °C and 0.10 M ionic strength by 1H NMR line broadening. Rate constants for cross-reactions calculated with use of this self-exchange rate in the Marcus relationship show good agreement with measured values. The effect of the paramagnetic ions [Cr(edta)]−, [Niiii, Me2L(1)]+, and [Cr(phen)3]3+on the ’H NMR relaxation rates of the cobalt(III) complex [ComMe2L(1)]+ has been used to investigate ion-pair structure in solution. These ion pairs serve as models for the electron-transfer precursor assemblies in the self-exchange reaction and two cross-reactions, respectively. Marcus calculations are relatively insensitive to the precursor structures. However, these structures provide a basis for interpretation of stereoselectivity data.

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Direct Determination of the Self-Exchange Rate of a Nickel(IV/III) Bis(oxime-imine) Complex. Investigation of Orientation Effects in Electron-Transfer Reactions

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