Kinetics and mechanism for intramolecular isomerization of HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 to Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9

Witold Paw; David K. Bower; David J. Bierdeman; Jerome B. Keister; Edward M. Schulman

doi:10.1080/00958979608024328

Kinetics and mechanism for intramolecular isomerization of HRu₃ (μ3-η³-EtSCCMeCMe)(CO)₉ to Ru₃(μ-SEt) (μ₃-η³-CCMeCHMe)(CO)₉

Witold Paw
, David K. Bower
, David J. Bierdeman
, Jerome B. Keister
, Edward M. Schulman

Chemistry

SUNY Buffalo
Buffalo State College, State University of New York

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

2 Scopus citations

Abstract

The kinetics for isomerization of HRu₃(μ₃-η³-EtSCCMeCMe)(CO)₉ to Ru₃(μ-SEt)(μ₃-η³-CCMeCHMe)(CO) ₉ were determined. The overall process involves C-H elimination, C-S and Ru-Ru bond cleavage and Ru₂(μ,-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH^‡ = 127(3) kJ/mol, ΔS^‡= 56(11) J/mol-K) and from the pressure dependence (0-207 MPa, ΔV^‡₀ +12.7(1.1) cm³/mol, Δβ^‡ = +0.037(0.012) cm³/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metalmetal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C-H elimination alone and CO dissociation is not involved.

Original language	English
Pages (from-to)	199-210
Number of pages	12
Journal	Journal of Coordination Chemistry
Volume	39
Issue number	3-4
DOIs	https://doi.org/10.1080/00958979608024328
State	Published - 1996

Keywords

Isomerization
Kinetics
Mechanism
Transition metal cluster
Volume of activation

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title = "Kinetics and mechanism for intramolecular isomerization of HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 to Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9",

abstract = "The kinetics for isomerization of HRu3(μ3-η3-EtSCCMeCMe)(CO)9 to Ru3(μ-SEt)(μ3-η3-CCMeCHMe)(CO) 9 were determined. The overall process involves C-H elimination, C-S and Ru-Ru bond cleavage and Ru2(μ,-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH‡ = 127(3) kJ/mol, ΔS‡= 56(11) J/mol-K) and from the pressure dependence (0-207 MPa, ΔV‡0 +12.7(1.1) cm3/mol, Δβ‡ = +0.037(0.012) cm3/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metalmetal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C-H elimination alone and CO dissociation is not involved.",

keywords = "Isomerization, Kinetics, Mechanism, Transition metal cluster, Volume of activation",

author = "Witold Paw and Bower, \{David K.\} and Bierdeman, \{David J.\} and Keister, \{Jerome B.\} and Schulman, \{Edward M.\}",

year = "1996",

doi = "10.1080/00958979608024328",

language = "English",

volume = "39",

pages = "199--210",

journal = "Journal of Coordination Chemistry",

issn = "0095-8972",

publisher = "Taylor and Francis Ltd.",

number = "3-4",

}

TY - JOUR

T1 - Kinetics and mechanism for intramolecular isomerization of HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 to Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9

AU - Paw, Witold

AU - Bower, David K.

AU - Bierdeman, David J.

AU - Keister, Jerome B.

AU - Schulman, Edward M.

PY - 1996

Y1 - 1996

N2 - The kinetics for isomerization of HRu3(μ3-η3-EtSCCMeCMe)(CO)9 to Ru3(μ-SEt)(μ3-η3-CCMeCHMe)(CO) 9 were determined. The overall process involves C-H elimination, C-S and Ru-Ru bond cleavage and Ru2(μ,-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH‡ = 127(3) kJ/mol, ΔS‡= 56(11) J/mol-K) and from the pressure dependence (0-207 MPa, ΔV‡0 +12.7(1.1) cm3/mol, Δβ‡ = +0.037(0.012) cm3/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metalmetal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C-H elimination alone and CO dissociation is not involved.

AB - The kinetics for isomerization of HRu3(μ3-η3-EtSCCMeCMe)(CO)9 to Ru3(μ-SEt)(μ3-η3-CCMeCHMe)(CO) 9 were determined. The overall process involves C-H elimination, C-S and Ru-Ru bond cleavage and Ru2(μ,-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH‡ = 127(3) kJ/mol, ΔS‡= 56(11) J/mol-K) and from the pressure dependence (0-207 MPa, ΔV‡0 +12.7(1.1) cm3/mol, Δβ‡ = +0.037(0.012) cm3/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metalmetal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C-H elimination alone and CO dissociation is not involved.

KW - Isomerization

KW - Kinetics

KW - Mechanism

KW - Transition metal cluster

KW - Volume of activation

UR - https://www.scopus.com/pages/publications/0347621227

U2 - 10.1080/00958979608024328

DO - 10.1080/00958979608024328

M3 - Article

AN - SCOPUS:0347621227

SN - 0095-8972

VL - 39

SP - 199

EP - 210

JO - Journal of Coordination Chemistry

JF - Journal of Coordination Chemistry

IS - 3-4

ER -

Kinetics and mechanism for intramolecular isomerization of HRu₃ (μ3-η³-EtSCCMeCMe)(CO)₉ to Ru₃(μ-SEt) (μ₃-η³-CCMeCHMe)(CO)₉

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Keywords

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