Resumen
The UV irradiation of [Re(η5-C5Me5)(CO)3] in the presence of C6F6 effected intermolecular C-F and intramolecular C-H activation generating [Re(η6-C5Me4CH2)(CO) 2(C6F5)] 1a in two isomeric forms. In the major isomer the CH2 group lies trans to the C6F5 group both in solution and in the crystal. In the minor isomer the CH2 lies cis to the C6F5 group. A similar reaction with C6F5CF3 generates [Re(η6-C5Me4CH2)(CO) 2(C6F4CF3)] 1b in four isomeric forms. In the major form the CF3 group is in the 4 position and the CH2 group lies trans to the C6F4CF3 group. The other three isomers are formed by rotation of the η6-C5Me4CH2 ligand as above, by placing the CF3 at the 3 position, and by a combination of the two. Complex 1a reacted with PMe3 to form the zwitterionic complex [Re(η5-C5Me4CH2PMe 3)(CO)2(C6F5)] and with MeO- to form the anion [Re(η5-C5Me4CH2OMe)(CO) 2(C6F5)]-, isolable as the NEt4+ salt. The reaction of 1a with HX (X = Cl or Br) generated cis-[Re(η5-C5Me5)(CO)2(C 6F5)X] initially. More prolonged reaction led to the trans isomers. On reaction with HI, only the trans isomer was formed. Reaction of 1a with HBF4 in Et2O in the presence of MeCN led to formation of the salt [Re(η5-C5Me5)(CO)2(C 6F5)(NCMe)]+[BF4]-. The halogens Cl2, Br2 and I2 reacted to form (halogenomethyl)tetramethylcyclopentadienyl complexes trans-[Re(η5-C5Me4CH2X)(CO) 2(C6F5)X] (X = Cl, Br or I). The bromo complex has been characterized crystallographically.
| Idioma original | English |
|---|---|
| Páginas (desde-hasta) | 3079-3086 |
| Número de páginas | 8 |
| Publicación | Journal of the Chemical Society - Dalton Transactions |
| N.º | 18 |
| DOI | |
| Estado | Published - 21 sep 1998 |
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ASJC Scopus subject areas
- Chemistry(all)
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Synthesis and reactions of the rhenium fulvene complexes [Re(η6-C5Me4CH2)(CO) 2(C6F4R)] (R = F or CF3) : Products derived from initial C-F activation. / Klahn, A. Hugo; Oelckers, Beatriz; Godoy, Fernando; Garland, Maria T.; Vega, Andres; Perutz, Robin N.; Higgitt, Catherine L.
En: Journal of the Chemical Society - Dalton Transactions, N.º 18, 21.09.1998, p. 3079-3086.Resultado de la investigación: Article
TY - JOUR
T1 - Synthesis and reactions of the rhenium fulvene complexes [Re(η6-C5Me4CH2)(CO) 2(C6F4R)] (R = F or CF3)
T2 - Products derived from initial C-F activation
AU - Klahn, A. Hugo
AU - Oelckers, Beatriz
AU - Godoy, Fernando
AU - Garland, Maria T.
AU - Vega, Andres
AU - Perutz, Robin N.
AU - Higgitt, Catherine L.
PY - 1998/9/21
Y1 - 1998/9/21
N2 - The UV irradiation of [Re(η5-C5Me5)(CO)3] in the presence of C6F6 effected intermolecular C-F and intramolecular C-H activation generating [Re(η6-C5Me4CH2)(CO) 2(C6F5)] 1a in two isomeric forms. In the major isomer the CH2 group lies trans to the C6F5 group both in solution and in the crystal. In the minor isomer the CH2 lies cis to the C6F5 group. A similar reaction with C6F5CF3 generates [Re(η6-C5Me4CH2)(CO) 2(C6F4CF3)] 1b in four isomeric forms. In the major form the CF3 group is in the 4 position and the CH2 group lies trans to the C6F4CF3 group. The other three isomers are formed by rotation of the η6-C5Me4CH2 ligand as above, by placing the CF3 at the 3 position, and by a combination of the two. Complex 1a reacted with PMe3 to form the zwitterionic complex [Re(η5-C5Me4CH2PMe 3)(CO)2(C6F5)] and with MeO- to form the anion [Re(η5-C5Me4CH2OMe)(CO) 2(C6F5)]-, isolable as the NEt4+ salt. The reaction of 1a with HX (X = Cl or Br) generated cis-[Re(η5-C5Me5)(CO)2(C 6F5)X] initially. More prolonged reaction led to the trans isomers. On reaction with HI, only the trans isomer was formed. Reaction of 1a with HBF4 in Et2O in the presence of MeCN led to formation of the salt [Re(η5-C5Me5)(CO)2(C 6F5)(NCMe)]+[BF4]-. The halogens Cl2, Br2 and I2 reacted to form (halogenomethyl)tetramethylcyclopentadienyl complexes trans-[Re(η5-C5Me4CH2X)(CO) 2(C6F5)X] (X = Cl, Br or I). The bromo complex has been characterized crystallographically.
AB - The UV irradiation of [Re(η5-C5Me5)(CO)3] in the presence of C6F6 effected intermolecular C-F and intramolecular C-H activation generating [Re(η6-C5Me4CH2)(CO) 2(C6F5)] 1a in two isomeric forms. In the major isomer the CH2 group lies trans to the C6F5 group both in solution and in the crystal. In the minor isomer the CH2 lies cis to the C6F5 group. A similar reaction with C6F5CF3 generates [Re(η6-C5Me4CH2)(CO) 2(C6F4CF3)] 1b in four isomeric forms. In the major form the CF3 group is in the 4 position and the CH2 group lies trans to the C6F4CF3 group. The other three isomers are formed by rotation of the η6-C5Me4CH2 ligand as above, by placing the CF3 at the 3 position, and by a combination of the two. Complex 1a reacted with PMe3 to form the zwitterionic complex [Re(η5-C5Me4CH2PMe 3)(CO)2(C6F5)] and with MeO- to form the anion [Re(η5-C5Me4CH2OMe)(CO) 2(C6F5)]-, isolable as the NEt4+ salt. The reaction of 1a with HX (X = Cl or Br) generated cis-[Re(η5-C5Me5)(CO)2(C 6F5)X] initially. More prolonged reaction led to the trans isomers. On reaction with HI, only the trans isomer was formed. Reaction of 1a with HBF4 in Et2O in the presence of MeCN led to formation of the salt [Re(η5-C5Me5)(CO)2(C 6F5)(NCMe)]+[BF4]-. The halogens Cl2, Br2 and I2 reacted to form (halogenomethyl)tetramethylcyclopentadienyl complexes trans-[Re(η5-C5Me4CH2X)(CO) 2(C6F5)X] (X = Cl, Br or I). The bromo complex has been characterized crystallographically.
UR - http://www.scopus.com/inward/record.url?scp=33749103424&partnerID=8YFLogxK
U2 - 10.1039/a802899k
DO - 10.1039/a802899k
M3 - Article
AN - SCOPUS:33749103424
SP - 3079
EP - 3086
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
SN - 1472-7773
IS - 18
ER -