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

Research output: Contribution to journal › Article

32 Scopus citations

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

Access to Document

10.1021/ic50226a026

Fingerprint Dive into the research topics of 'Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles'. Together they form a unique fingerprint.

Cite this

Balahura, R. J., & Purcell, W. L. (1981). Neighboring-Group Participation in the Hydrolysis of Coordinated Nitriles. Inorganic Chemistry, 20(12), 4159-4163. https://doi.org/10.1021/ic50226a026

@article{590bfbfa9a5840b48147b83a67bd44b2,

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.",

author = "Balahura, {Robert J.} and Purcell, {W. L.}",

year = "1981",

month = dec,

doi = "10.1021/ic50226a026",

language = "English (US)",

volume = "20",

pages = "4159--4163",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

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

AU - Balahura, Robert J.

AU - Purcell, W. L.

PY - 1981/12

Y1 - 1981/12

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.

UR - http://www.scopus.com/inward/record.url?scp=0001044638&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001044638&partnerID=8YFLogxK

U2 - 10.1021/ic50226a026

DO - 10.1021/ic50226a026

M3 - Article

AN - SCOPUS:0001044638

VL - 20

SP - 4159

EP - 4163

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 12

ER -