Volumes of Activation for the Cycloaddition Reactions of Phenylhalocarbenes to Alkenes

Nicholas J. Turro; Masami Okamoto; Ian R. Gould; Robert A. Moss; Witold Ławrynowicz; Linda M. Hadel

doi:10.1021/ja00250a035

Volumes of Activation for the Cycloaddition Reactions of Phenylhalocarbenes to Alkenes

Nicholas J. Turro, Masami Okamoto, Ian R. Gould, Robert A. Moss, Witold Ławrynowicz, Linda M. Hadel

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

22 Scopus citations

Abstract

The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPa. In all cases the observed rate constants were found to increase with increasing pressure. The magnitude of the derived activation volumes falls in the range of-10 to -18 cm³/mol and does not depend on solvent. The results rule out a late, two-bond transition state and a bipolar single-bond transition state but are consistent with the reversible formation of a carbene-alkene complex or an early one- or two-bond transition state.

Original language	English (US)
Pages (from-to)	4973-4976
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	109
Issue number	16
DOIs	https://doi.org/10.1021/ja00250a035
State	Published - Aug 1 1987
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja00250a035

Cite this

@article{b9d4fc62c6154f29a84a1fefa90b2773,

title = "Volumes of Activation for the Cycloaddition Reactions of Phenylhalocarbenes to Alkenes",

abstract = "The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPa. In all cases the observed rate constants were found to increase with increasing pressure. The magnitude of the derived activation volumes falls in the range of-10 to -18 cm3/mol and does not depend on solvent. The results rule out a late, two-bond transition state and a bipolar single-bond transition state but are consistent with the reversible formation of a carbene-alkene complex or an early one- or two-bond transition state.",

author = "Turro, {Nicholas J.} and Masami Okamoto and Gould, {Ian R.} and Moss, {Robert A.} and Witold {\L}awrynowicz and Hadel, {Linda M.}",

year = "1987",

month = aug,

day = "1",

doi = "10.1021/ja00250a035",

language = "English (US)",

volume = "109",

pages = "4973--4976",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Volumes of Activation for the Cycloaddition Reactions of Phenylhalocarbenes to Alkenes

AU - Turro, Nicholas J.

AU - Okamoto, Masami

AU - Gould, Ian R.

AU - Moss, Robert A.

AU - Ławrynowicz, Witold

AU - Hadel, Linda M.

PY - 1987/8/1

Y1 - 1987/8/1

N2 - The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPa. In all cases the observed rate constants were found to increase with increasing pressure. The magnitude of the derived activation volumes falls in the range of-10 to -18 cm3/mol and does not depend on solvent. The results rule out a late, two-bond transition state and a bipolar single-bond transition state but are consistent with the reversible formation of a carbene-alkene complex or an early one- or two-bond transition state.

AB - The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPa. In all cases the observed rate constants were found to increase with increasing pressure. The magnitude of the derived activation volumes falls in the range of-10 to -18 cm3/mol and does not depend on solvent. The results rule out a late, two-bond transition state and a bipolar single-bond transition state but are consistent with the reversible formation of a carbene-alkene complex or an early one- or two-bond transition state.

UR - http://www.scopus.com/inward/record.url?scp=0348020008&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0348020008&partnerID=8YFLogxK

U2 - 10.1021/ja00250a035

DO - 10.1021/ja00250a035

M3 - Article

AN - SCOPUS:0348020008

SN - 0002-7863

VL - 109

SP - 4973

EP - 4976

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 16

ER -

Volumes of Activation for the Cycloaddition Reactions of Phenylhalocarbenes to Alkenes

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this