Deamination of 2-Methyl-2-propanamine Induced by Hydroxyl Radicals and Metal Ions: A Comparison between the Rates of β Elimination of Ammonia and Water

Sara Goldstein; Gidon Czapski; Haim Cohen; Dan Meyerstein; Jeoung Ki Cho; Sason S. Shaik

doi:10.1021/ic00031a020

Deamination of 2-Methyl-2-propanamine Induced by Hydroxyl Radicals and Metal Ions: A Comparison between the Rates of β Elimination of Ammonia and Water

Sara Goldstein, Gidon Czapski, Haim Cohen, Dan Meyerstein, Jeoung Ki Cho, Sason S. Shaik

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Abstract

The reactions of CH₂C(CH₃)₂NH₃with Cu⁺(aq) and Cr(H₂O)₆²⁺were studied using the pulse radiolysis technique. The formation of the unstable [Cu^II-CH₂C(CH₃)₂(NH₃⁺)]⁺and [(H₂O)_sCr^III-CH₂C(CH₃)₂(NH₃⁺)]²⁺ions was observed in these reactions. These complexes decompose via /S elimination of NH₃to yield 2-methylpropene, ammonia, and Cu²⁺(aq) or Cr³⁺(aq). The rates of these β-elimination reactions are considerably slower than those of the analogous β-hydroxyl elimination. It is suggested that the rates of the β-elimination processes are correlated to the strengths of the C-O and C-N bonds, which are cleaved in these reactions. A valence-bond analysis coupled with some ab-initio SCF-MO computations explains the effect of protonation on these bond strengths.

Original language	English
Pages (from-to)	798-803
Number of pages	6
Journal	Inorganic Chemistry
Volume	31
Issue number	5
DOIs	https://doi.org/10.1021/ic00031a020
State	Published - 1 Mar 1992
Externally published	Yes

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title = "Deamination of 2-Methyl-2-propanamine Induced by Hydroxyl Radicals and Metal Ions: A Comparison between the Rates of β Elimination of Ammonia and Water",

abstract = "The reactions of CH2C(CH3)2NH3with Cu+(aq) and Cr(H2O)62+were studied using the pulse radiolysis technique. The formation of the unstable [CuII-CH2C(CH3)2(NH3+)]+and [(H2O)sCrIII-CH2C(CH3)2(NH3+)]2+ions was observed in these reactions. These complexes decompose via /S elimination of NH3to yield 2-methylpropene, ammonia, and Cu2+(aq) or Cr3+(aq). The rates of these β-elimination reactions are considerably slower than those of the analogous β-hydroxyl elimination. It is suggested that the rates of the β-elimination processes are correlated to the strengths of the C-O and C-N bonds, which are cleaved in these reactions. A valence-bond analysis coupled with some ab-initio SCF-MO computations explains the effect of protonation on these bond strengths.",

author = "Sara Goldstein and Gidon Czapski and Haim Cohen and Dan Meyerstein and Cho, {Jeoung Ki} and Shaik, {Sason S.}",

year = "1992",

month = mar,

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doi = "10.1021/ic00031a020",

language = "אנגלית",

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T2 - A Comparison between the Rates of β Elimination of Ammonia and Water

AU - Goldstein, Sara

AU - Czapski, Gidon

AU - Cohen, Haim

AU - Meyerstein, Dan

AU - Cho, Jeoung Ki

AU - Shaik, Sason S.

PY - 1992/3/1

Y1 - 1992/3/1

N2 - The reactions of CH2C(CH3)2NH3with Cu+(aq) and Cr(H2O)62+were studied using the pulse radiolysis technique. The formation of the unstable [CuII-CH2C(CH3)2(NH3+)]+and [(H2O)sCrIII-CH2C(CH3)2(NH3+)]2+ions was observed in these reactions. These complexes decompose via /S elimination of NH3to yield 2-methylpropene, ammonia, and Cu2+(aq) or Cr3+(aq). The rates of these β-elimination reactions are considerably slower than those of the analogous β-hydroxyl elimination. It is suggested that the rates of the β-elimination processes are correlated to the strengths of the C-O and C-N bonds, which are cleaved in these reactions. A valence-bond analysis coupled with some ab-initio SCF-MO computations explains the effect of protonation on these bond strengths.

AB - The reactions of CH2C(CH3)2NH3with Cu+(aq) and Cr(H2O)62+were studied using the pulse radiolysis technique. The formation of the unstable [CuII-CH2C(CH3)2(NH3+)]+and [(H2O)sCrIII-CH2C(CH3)2(NH3+)]2+ions was observed in these reactions. These complexes decompose via /S elimination of NH3to yield 2-methylpropene, ammonia, and Cu2+(aq) or Cr3+(aq). The rates of these β-elimination reactions are considerably slower than those of the analogous β-hydroxyl elimination. It is suggested that the rates of the β-elimination processes are correlated to the strengths of the C-O and C-N bonds, which are cleaved in these reactions. A valence-bond analysis coupled with some ab-initio SCF-MO computations explains the effect of protonation on these bond strengths.

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Deamination of 2-Methyl-2-propanamine Induced by Hydroxyl Radicals and Metal Ions: A Comparison between the Rates of β Elimination of Ammonia and Water

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