Abstract
The majority of stable low valent transition metal organometallic complexes obey the familiar eighteen-electron rule. Oxidative addition reactions of these complexes normally proceed by initial generation of sixteen electron coordinatively unsaturated species. Low valent 17 electron transition metal radical complexes ®ML(n) can be generated thermally or photochemically. Since radical recombination to form metal-metal bonded dimers L(n)M-ML(n) is a rapid process, the absolute concentration of metal radicals that can be achieved in solution is normally quite low. In cases where either there is no stable metal-metal bonded dimer or the metal-metal bond is so weak that the complex is completely dissociated in solution, relatively high concentrations (ca. 1 mM) are readily achieved. Illustrative mechanisms for oxidative addition reactions of ®ML(n) are discussed with a focus on reaction mechanisms that are second order in total metal concentration. (C) 2000 Elsevier Science S.A.
| Original language | English |
|---|---|
| Pages (from-to) | 451-467 |
| Number of pages | 17 |
| Journal | Coordination Chemistry Reviews |
| Volume | 206-207 |
| DOIs | |
| State | Published - Oct 17 2000 |
Fingerprint
Keywords
- Kinetic
- Thermodynamic
- Transition metal radical
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Thermodynamic and kinetic studies of stable low valent transition metal radical complexes. / Hoff, Carl.
In: Coordination Chemistry Reviews, Vol. 206-207, 17.10.2000, p. 451-467.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Thermodynamic and kinetic studies of stable low valent transition metal radical complexes
AU - Hoff, Carl
PY - 2000/10/17
Y1 - 2000/10/17
N2 - The majority of stable low valent transition metal organometallic complexes obey the familiar eighteen-electron rule. Oxidative addition reactions of these complexes normally proceed by initial generation of sixteen electron coordinatively unsaturated species. Low valent 17 electron transition metal radical complexes ®ML(n) can be generated thermally or photochemically. Since radical recombination to form metal-metal bonded dimers L(n)M-ML(n) is a rapid process, the absolute concentration of metal radicals that can be achieved in solution is normally quite low. In cases where either there is no stable metal-metal bonded dimer or the metal-metal bond is so weak that the complex is completely dissociated in solution, relatively high concentrations (ca. 1 mM) are readily achieved. Illustrative mechanisms for oxidative addition reactions of ®ML(n) are discussed with a focus on reaction mechanisms that are second order in total metal concentration. (C) 2000 Elsevier Science S.A.
AB - The majority of stable low valent transition metal organometallic complexes obey the familiar eighteen-electron rule. Oxidative addition reactions of these complexes normally proceed by initial generation of sixteen electron coordinatively unsaturated species. Low valent 17 electron transition metal radical complexes ®ML(n) can be generated thermally or photochemically. Since radical recombination to form metal-metal bonded dimers L(n)M-ML(n) is a rapid process, the absolute concentration of metal radicals that can be achieved in solution is normally quite low. In cases where either there is no stable metal-metal bonded dimer or the metal-metal bond is so weak that the complex is completely dissociated in solution, relatively high concentrations (ca. 1 mM) are readily achieved. Illustrative mechanisms for oxidative addition reactions of ®ML(n) are discussed with a focus on reaction mechanisms that are second order in total metal concentration. (C) 2000 Elsevier Science S.A.
KW - Kinetic
KW - Thermodynamic
KW - Transition metal radical
UR - http://www.scopus.com/inward/record.url?scp=0033798875&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0033798875&partnerID=8YFLogxK
U2 - 10.1016/S0010-8545(00)00337-4
DO - 10.1016/S0010-8545(00)00337-4
M3 - Article
VL - 206-207
SP - 451
EP - 467
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
SN - 0010-8545
ER -