Abstract
Based on the PCN ligand 2, a remarkable degree of control over C-C versus C-H bond activation and versus formation of an agostic C-C complex was demonstrated by choice of cationic [Rh(CO)n(C2H 4)2-n] (n=0, 1, 2) precursors. Whereas reaction of 2 with [Rh(C2H4)2(solv)n]BF4 results in exclusive C-C bond activation to yield product 5, reaction with the dicarbonyl precursor [Rh(CO)2(solv)n]BF4 leads to formation of the C-H activated complex 9. The latter process is promoted by intramolecular deprotonation of the C-H bond by the hemilabile amine arm of the PCN ligand. The mixed monocarbonyl monoethylene Rh species [Rh(CO)(C 2H4)]BF4 reacts with the PCN ligand 2 to give an agostic complex 7. The C-C activated complex 5 is easily converted to the C-H activated one (9) by reaction with CO; the reaction proceeds by a unique sequence of 1,2-metal-to-carbon methyl shift, agostic interaction, and C-H activation processes. Similarly, the C-C agostic complex 7 is converted to the same C-H activated product 9 by treatment with CO.
| Original language | English |
|---|---|
| Pages (from-to) | 4295-4300 |
| Number of pages | 6 |
| Journal | Chemistry - A European Journal |
| Volume | 9 |
| Issue number | 18 |
| DOIs | |
| Publication status | Published - Sep 22 2003 |
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Keywords
- Agostic interactions
- C-C activation
- C-H activation
- Carbonyl ligands
- Dearomatization
- Tridentate ligands
ASJC Scopus subject areas
- Chemistry(all)
Cite this
C-C versus C-H activation and versus agostic C-C interaction controlled by electron density at the metal center. / Gandelman, Mark; Shimon, Linda J W; Milstein, David.
In: Chemistry - A European Journal, Vol. 9, No. 18, 22.09.2003, p. 4295-4300.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - C-C versus C-H activation and versus agostic C-C interaction controlled by electron density at the metal center
AU - Gandelman, Mark
AU - Shimon, Linda J W
AU - Milstein, David
PY - 2003/9/22
Y1 - 2003/9/22
N2 - Based on the PCN ligand 2, a remarkable degree of control over C-C versus C-H bond activation and versus formation of an agostic C-C complex was demonstrated by choice of cationic [Rh(CO)n(C2H 4)2-n] (n=0, 1, 2) precursors. Whereas reaction of 2 with [Rh(C2H4)2(solv)n]BF4 results in exclusive C-C bond activation to yield product 5, reaction with the dicarbonyl precursor [Rh(CO)2(solv)n]BF4 leads to formation of the C-H activated complex 9. The latter process is promoted by intramolecular deprotonation of the C-H bond by the hemilabile amine arm of the PCN ligand. The mixed monocarbonyl monoethylene Rh species [Rh(CO)(C 2H4)]BF4 reacts with the PCN ligand 2 to give an agostic complex 7. The C-C activated complex 5 is easily converted to the C-H activated one (9) by reaction with CO; the reaction proceeds by a unique sequence of 1,2-metal-to-carbon methyl shift, agostic interaction, and C-H activation processes. Similarly, the C-C agostic complex 7 is converted to the same C-H activated product 9 by treatment with CO.
AB - Based on the PCN ligand 2, a remarkable degree of control over C-C versus C-H bond activation and versus formation of an agostic C-C complex was demonstrated by choice of cationic [Rh(CO)n(C2H 4)2-n] (n=0, 1, 2) precursors. Whereas reaction of 2 with [Rh(C2H4)2(solv)n]BF4 results in exclusive C-C bond activation to yield product 5, reaction with the dicarbonyl precursor [Rh(CO)2(solv)n]BF4 leads to formation of the C-H activated complex 9. The latter process is promoted by intramolecular deprotonation of the C-H bond by the hemilabile amine arm of the PCN ligand. The mixed monocarbonyl monoethylene Rh species [Rh(CO)(C 2H4)]BF4 reacts with the PCN ligand 2 to give an agostic complex 7. The C-C activated complex 5 is easily converted to the C-H activated one (9) by reaction with CO; the reaction proceeds by a unique sequence of 1,2-metal-to-carbon methyl shift, agostic interaction, and C-H activation processes. Similarly, the C-C agostic complex 7 is converted to the same C-H activated product 9 by treatment with CO.
KW - Agostic interactions
KW - C-C activation
KW - C-H activation
KW - Carbonyl ligands
KW - Dearomatization
KW - Tridentate ligands
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UR - http://www.scopus.com/inward/citedby.url?scp=0141868817&partnerID=8YFLogxK
U2 - 10.1002/chem.200304972
DO - 10.1002/chem.200304972
M3 - Article
VL - 9
SP - 4295
EP - 4300
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 18
ER -