The Cyclopentylpentaaquochromium(III) Ion: Synthesis, Characterization, and Kinetics of Acidolysis, Homolysis, and Electrophilic Cleavage Reactions

James H. Espenson; Philip Connolly; Dan Meyerstein; Haim Cohen

doi:10.1021/ic00149a001

The Cyclopentylpentaaquochromium(III) Ion: Synthesis, Characterization, and Kinetics of Acidolysis, Homolysis, and Electrophilic Cleavage Reactions

James H. Espenson, Philip Connolly, Dan Meyerstein, Haim Cohen

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

24 Scopus citations

Abstract

The complex [(H20)5Cr-c-C5H9]2+ is formed in the reaction of Cr2+ with H202 in aqueous solution saturated with cyclopentane. Reaction of Cr2+ with cyclopentyl radical, a step observed directly by pulse radiolysis (k = (8.0 - 1.0) X 107 M-1 s-1), yields (H20)5Cr-c-C5H92+, the radical being formed by abstraction from the hydrocarbon with HO·. The complex was isolated chromatographically and characterized by its absorption spectrum and the products of reactions (C5H9Br from. Br2, C5H9OH from homolysis in the presence of Fe3+ and Cu2+). It decomposes by parallel unimolecular pathways of acidolysis [formula-omitted] and homolysis [formula-omitted], although the latter is a reversible and thermodynamically unfavorable process, which occurs only in the presence of oxidizing agents. The complex also reacts in bimolecular displacement reactions (SE2 mechanism) with [formula-omitted], and [formula-omitted].

Original language	English
Pages (from-to)	1009-1013
Number of pages	5
Journal	Inorganic Chemistry
Volume	22
Issue number	7
DOIs	https://doi.org/10.1021/ic00149a001
State	Published - Mar 1983
Externally published	Yes

Access to Document

10.1021/ic00149a001

Cite this

@article{514c2154ee5f4e9db5553c01880406d6,

title = "The Cyclopentylpentaaquochromium(III) Ion: Synthesis, Characterization, and Kinetics of Acidolysis, Homolysis, and Electrophilic Cleavage Reactions",

abstract = "The complex [(H20)5Cr-c-C5H9]2+ is formed in the reaction of Cr2+ with H202 in aqueous solution saturated with cyclopentane. Reaction of Cr2+ with cyclopentyl radical, a step observed directly by pulse radiolysis (k = (8.0 - 1.0) X 107 M-1 s-1), yields (H20)5Cr-c-C5H92+, the radical being formed by abstraction from the hydrocarbon with HO·. The complex was isolated chromatographically and characterized by its absorption spectrum and the products of reactions (C5H9Br from. Br2, C5H9OH from homolysis in the presence of Fe3+ and Cu2+). It decomposes by parallel unimolecular pathways of acidolysis [formula-omitted] and homolysis [formula-omitted], although the latter is a reversible and thermodynamically unfavorable process, which occurs only in the presence of oxidizing agents. The complex also reacts in bimolecular displacement reactions (SE2 mechanism) with [formula-omitted], and [formula-omitted].",

author = "Espenson, {James H.} and Philip Connolly and Dan Meyerstein and Haim Cohen",

year = "1983",

month = mar,

doi = "10.1021/ic00149a001",

language = "אנגלית",

volume = "22",

pages = "1009--1013",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - The Cyclopentylpentaaquochromium(III) Ion

T2 - Synthesis, Characterization, and Kinetics of Acidolysis, Homolysis, and Electrophilic Cleavage Reactions

AU - Espenson, James H.

AU - Connolly, Philip

AU - Meyerstein, Dan

AU - Cohen, Haim

PY - 1983/3

Y1 - 1983/3

N2 - The complex [(H20)5Cr-c-C5H9]2+ is formed in the reaction of Cr2+ with H202 in aqueous solution saturated with cyclopentane. Reaction of Cr2+ with cyclopentyl radical, a step observed directly by pulse radiolysis (k = (8.0 - 1.0) X 107 M-1 s-1), yields (H20)5Cr-c-C5H92+, the radical being formed by abstraction from the hydrocarbon with HO·. The complex was isolated chromatographically and characterized by its absorption spectrum and the products of reactions (C5H9Br from. Br2, C5H9OH from homolysis in the presence of Fe3+ and Cu2+). It decomposes by parallel unimolecular pathways of acidolysis [formula-omitted] and homolysis [formula-omitted], although the latter is a reversible and thermodynamically unfavorable process, which occurs only in the presence of oxidizing agents. The complex also reacts in bimolecular displacement reactions (SE2 mechanism) with [formula-omitted], and [formula-omitted].

AB - The complex [(H20)5Cr-c-C5H9]2+ is formed in the reaction of Cr2+ with H202 in aqueous solution saturated with cyclopentane. Reaction of Cr2+ with cyclopentyl radical, a step observed directly by pulse radiolysis (k = (8.0 - 1.0) X 107 M-1 s-1), yields (H20)5Cr-c-C5H92+, the radical being formed by abstraction from the hydrocarbon with HO·. The complex was isolated chromatographically and characterized by its absorption spectrum and the products of reactions (C5H9Br from. Br2, C5H9OH from homolysis in the presence of Fe3+ and Cu2+). It decomposes by parallel unimolecular pathways of acidolysis [formula-omitted] and homolysis [formula-omitted], although the latter is a reversible and thermodynamically unfavorable process, which occurs only in the presence of oxidizing agents. The complex also reacts in bimolecular displacement reactions (SE2 mechanism) with [formula-omitted], and [formula-omitted].

UR - http://www.scopus.com/inward/record.url?scp=4244094754&partnerID=8YFLogxK

U2 - 10.1021/ic00149a001

DO - 10.1021/ic00149a001

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

AN - SCOPUS:4244094754

SN - 0020-1669

VL - 22

SP - 1009

EP - 1013

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

The Cyclopentylpentaaquochromium(III) Ion: Synthesis, Characterization, and Kinetics of Acidolysis, Homolysis, and Electrophilic Cleavage Reactions

Abstract

Access to Document

Other files and links

Fingerprint

Cite this