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

A. Hugo Klahn, Beatriz Oelckers, Fernando Godoy, Maria T. Garland, Andres Vega, Robin N. Perutz, Catherine L. Higgitt

Resultado de la investigación: Article

46 Citas (Scopus)

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 originalEnglish
Páginas (desde-hasta)3079-3086
Número de páginas8
PublicaciónJournal of the Chemical Society - Dalton Transactions
N.º18
DOI
EstadoPublished - 21 sep 1998

Huella dactilar

Rhenium
Isomers
Chemical activation
Salts
Halogens
Anions
fulvene
Irradiation
Ligands
Crystals

ASJC Scopus subject areas

  • Chemistry(all)

Citar esto

Klahn, A. Hugo ; Oelckers, Beatriz ; Godoy, Fernando ; Garland, Maria T. ; Vega, Andres ; Perutz, Robin N. ; Higgitt, Catherine L. / 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. En: Journal of the Chemical Society - Dalton Transactions. 1998 ; N.º 18. pp. 3079-3086.
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title = "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",
abstract = "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.",
author = "Klahn, {A. Hugo} and Beatriz Oelckers and Fernando Godoy and Garland, {Maria T.} and Andres Vega and Perutz, {Robin N.} and Higgitt, {Catherine L.}",
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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.

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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 -