Abstract
Metal-promoted activation of C-C bonds in homogeneous media under mild conditions may lead to the design of new selective processes for the utilization of hydrocarbons. However, examples of C-C bond activation in solution are much more scarce than those of C-H bond activation. We looked at the available data on metal insertion into C-C bonds in solution and tried to answer some important questions regarding the C-C bond activation. What kind of ligated metal center is necessary in order to cleave the 'hidden' C-C bond? What are the possible mechanisms of the C-C activation in various reaction systems, and how do different metal centers influence the reactivity? How can one tune the metal center for C-C bond cleavage by varying the steric and electronic properties of ligands? Thermodynamically, insertion into a C-C bond in solution is not a forbidden process, even if no strain relief or aromatization driving force is involved. Moreover, with an appropriate system C-C activation may prevail thermodynamically and kinetically over the competing C-H activation. The relative thermodynamics of C-C versus C-H cleavage is influenced by the electron density on the metal center. When kinetics is concerned, coordinative unsaturation appears to be crucial for C-C oxidative addition.
| Original language | English |
|---|---|
| Pages (from-to) | 871-883 |
| Number of pages | 13 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 38 |
| Issue number | 7 |
| Publication status | Published - Apr 1 1999 |
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Keywords
- C-C activation
- C-H activation
- Homogeneous catalysis
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Metal insertion into C-C bonds in solution. / Rybtchinski, Boris; Milstein, David.
In: Angewandte Chemie - International Edition, Vol. 38, No. 7, 01.04.1999, p. 871-883.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Metal insertion into C-C bonds in solution
AU - Rybtchinski, Boris
AU - Milstein, David
PY - 1999/4/1
Y1 - 1999/4/1
N2 - Metal-promoted activation of C-C bonds in homogeneous media under mild conditions may lead to the design of new selective processes for the utilization of hydrocarbons. However, examples of C-C bond activation in solution are much more scarce than those of C-H bond activation. We looked at the available data on metal insertion into C-C bonds in solution and tried to answer some important questions regarding the C-C bond activation. What kind of ligated metal center is necessary in order to cleave the 'hidden' C-C bond? What are the possible mechanisms of the C-C activation in various reaction systems, and how do different metal centers influence the reactivity? How can one tune the metal center for C-C bond cleavage by varying the steric and electronic properties of ligands? Thermodynamically, insertion into a C-C bond in solution is not a forbidden process, even if no strain relief or aromatization driving force is involved. Moreover, with an appropriate system C-C activation may prevail thermodynamically and kinetically over the competing C-H activation. The relative thermodynamics of C-C versus C-H cleavage is influenced by the electron density on the metal center. When kinetics is concerned, coordinative unsaturation appears to be crucial for C-C oxidative addition.
AB - Metal-promoted activation of C-C bonds in homogeneous media under mild conditions may lead to the design of new selective processes for the utilization of hydrocarbons. However, examples of C-C bond activation in solution are much more scarce than those of C-H bond activation. We looked at the available data on metal insertion into C-C bonds in solution and tried to answer some important questions regarding the C-C bond activation. What kind of ligated metal center is necessary in order to cleave the 'hidden' C-C bond? What are the possible mechanisms of the C-C activation in various reaction systems, and how do different metal centers influence the reactivity? How can one tune the metal center for C-C bond cleavage by varying the steric and electronic properties of ligands? Thermodynamically, insertion into a C-C bond in solution is not a forbidden process, even if no strain relief or aromatization driving force is involved. Moreover, with an appropriate system C-C activation may prevail thermodynamically and kinetically over the competing C-H activation. The relative thermodynamics of C-C versus C-H cleavage is influenced by the electron density on the metal center. When kinetics is concerned, coordinative unsaturation appears to be crucial for C-C oxidative addition.
KW - C-C activation
KW - C-H activation
KW - Homogeneous catalysis
UR - http://www.scopus.com/inward/record.url?scp=0033119285&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0033119285&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0033119285
VL - 38
SP - 871
EP - 883
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 7
ER -