Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe

Richard K. Laidlaw; Yozo Miura; Janice L. Grant; Lalit Cooray; Matthew Clark; Lowell D. Kispert; Robert M. Metzger

doi:10.1063/1.452810

Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe

Richard K. Laidlaw, Yozo Miura, Janice L. Grant, Lalit Cooray, Matthew Clark, Lowell D. Kispert, Robert M. Metzger

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The donor DMAPCMe is found by theoretical calculations and cyclic voltammetry to be a moderate electron donor (calculated adiabatic ionization potential 7.17 eV, E_1/2 = 0.55 V vs SCE), which is intermediate between the experimental ionization energies of TMPD (6.25 eV), TTF (6.83 eV), and pyrene (7.41 eV). DMAPCMe is extensively hydrogen-bonded in solution, as seen by the growth of a shifted N-H infrared vibration band. The paramagnetic resonance spectrum of the DMAPCMe⁺ radical cation matches fairly well a simulated monomer radical spectrum, but there is evidence for H-bonded paramagnetic adducts. These same adducts reduce irreversibly at 0.37 V vs SCE in acetonitrile solution.

Original language	English
Pages (from-to)	4967-4971
Number of pages	5
Journal	The Journal of Chemical Physics
Volume	87
Issue number	8
DOIs	https://doi.org/10.1063/1.452810
State	Published - Jan 1 1987
Externally published	Yes

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title = "Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe",

abstract = "The donor DMAPCMe is found by theoretical calculations and cyclic voltammetry to be a moderate electron donor (calculated adiabatic ionization potential 7.17 eV, E1/2 = 0.55 V vs SCE), which is intermediate between the experimental ionization energies of TMPD (6.25 eV), TTF (6.83 eV), and pyrene (7.41 eV). DMAPCMe is extensively hydrogen-bonded in solution, as seen by the growth of a shifted N-H infrared vibration band. The paramagnetic resonance spectrum of the DMAPCMe+ radical cation matches fairly well a simulated monomer radical spectrum, but there is evidence for H-bonded paramagnetic adducts. These same adducts reduce irreversibly at 0.37 V vs SCE in acetonitrile solution.",

author = "Laidlaw, {Richard K.} and Yozo Miura and Grant, {Janice L.} and Lalit Cooray and Matthew Clark and Kispert, {Lowell D.} and Metzger, {Robert M.}",

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doi = "10.1063/1.452810",

language = "English",

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T1 - Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe

AU - Laidlaw, Richard K.

AU - Miura, Yozo

AU - Grant, Janice L.

AU - Cooray, Lalit

AU - Clark, Matthew

AU - Kispert, Lowell D.

AU - Metzger, Robert M.

PY - 1987/1/1

Y1 - 1987/1/1

N2 - The donor DMAPCMe is found by theoretical calculations and cyclic voltammetry to be a moderate electron donor (calculated adiabatic ionization potential 7.17 eV, E1/2 = 0.55 V vs SCE), which is intermediate between the experimental ionization energies of TMPD (6.25 eV), TTF (6.83 eV), and pyrene (7.41 eV). DMAPCMe is extensively hydrogen-bonded in solution, as seen by the growth of a shifted N-H infrared vibration band. The paramagnetic resonance spectrum of the DMAPCMe+ radical cation matches fairly well a simulated monomer radical spectrum, but there is evidence for H-bonded paramagnetic adducts. These same adducts reduce irreversibly at 0.37 V vs SCE in acetonitrile solution.

AB - The donor DMAPCMe is found by theoretical calculations and cyclic voltammetry to be a moderate electron donor (calculated adiabatic ionization potential 7.17 eV, E1/2 = 0.55 V vs SCE), which is intermediate between the experimental ionization energies of TMPD (6.25 eV), TTF (6.83 eV), and pyrene (7.41 eV). DMAPCMe is extensively hydrogen-bonded in solution, as seen by the growth of a shifted N-H infrared vibration band. The paramagnetic resonance spectrum of the DMAPCMe+ radical cation matches fairly well a simulated monomer radical spectrum, but there is evidence for H-bonded paramagnetic adducts. These same adducts reduce irreversibly at 0.37 V vs SCE in acetonitrile solution.

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DO - 10.1063/1.452810

M3 - Article

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JO - The Journal of Chemical Physics

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Hydrogen bonding and cation radical formation of methyl 4-(N,N-dimethylamino)phenyl carbamate, DMAPCMe

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