Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles

Robert J. Balahura; W. L. Purcell

doi:10.1021/ic50226a026

Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles

Robert J. Balahura, W. L. Purcell

Chemistry

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Abstract

The hydrolysis reaction (Chemical Equation Presented) has been studied. For R = CN, k_h = 1050 ± 60 M^-1 s^-1, ΔH‡ = 13.6 ± 0.5 kcal mol^-1, ΔS‡ = 1.0 ± 2 eu at 25°C, and I = 1.0 M (LiClO₄). For R = CONH₂, k_h = (5.8 ± 0.5) × 10⁶ M^-1 s^-1, ΔH‡ = 21.3 ± 0.5 kcal mol^-1, ΔS‡ = 44 ± 2 eu at 25°C, and I = 1.0 M (LiClO₄). The unusual kinetic parameters for the latter complex are attributed to neighboring-group participation by the amide group.

Original language	English (US)
Pages (from-to)	4159-4163
Number of pages	5
Journal	Inorganic Chemistry
Volume	20
Issue number	12
DOIs	https://doi.org/10.1021/ic50226a026
State	Published - Dec 1981

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles",

abstract = "The hydrolysis reaction (Chemical Equation Presented) has been studied. For R = CN, kh = 1050 ± 60 M-1 s-1, ΔH‡ = 13.6 ± 0.5 kcal mol-1, ΔS‡ = 1.0 ± 2 eu at 25°C, and I = 1.0 M (LiClO4). For R = CONH2, kh = (5.8 ± 0.5) × 106 M-1 s-1, ΔH‡ = 21.3 ± 0.5 kcal mol-1, ΔS‡ = 44 ± 2 eu at 25°C, and I = 1.0 M (LiClO4). The unusual kinetic parameters for the latter complex are attributed to neighboring-group participation by the amide group.",

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year = "1981",

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T1 - Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles

AU - Balahura, Robert J.

AU - Purcell, W. L.

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N2 - The hydrolysis reaction (Chemical Equation Presented) has been studied. For R = CN, kh = 1050 ± 60 M-1 s-1, ΔH‡ = 13.6 ± 0.5 kcal mol-1, ΔS‡ = 1.0 ± 2 eu at 25°C, and I = 1.0 M (LiClO4). For R = CONH2, kh = (5.8 ± 0.5) × 106 M-1 s-1, ΔH‡ = 21.3 ± 0.5 kcal mol-1, ΔS‡ = 44 ± 2 eu at 25°C, and I = 1.0 M (LiClO4). The unusual kinetic parameters for the latter complex are attributed to neighboring-group participation by the amide group.

AB - The hydrolysis reaction (Chemical Equation Presented) has been studied. For R = CN, kh = 1050 ± 60 M-1 s-1, ΔH‡ = 13.6 ± 0.5 kcal mol-1, ΔS‡ = 1.0 ± 2 eu at 25°C, and I = 1.0 M (LiClO4). For R = CONH2, kh = (5.8 ± 0.5) × 106 M-1 s-1, ΔH‡ = 21.3 ± 0.5 kcal mol-1, ΔS‡ = 44 ± 2 eu at 25°C, and I = 1.0 M (LiClO4). The unusual kinetic parameters for the latter complex are attributed to neighboring-group participation by the amide group.

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Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles

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