36630-33-8Relevant academic research and scientific papers
Isomerization pathways of (acylcycloheptatriene)iron tricarbonyl complexes
Williams, Gregory M.,Pino, Mark J.
, p. 345 - 349 (2008/10/08)
The (7-exo-acylcycloheptatriene)Fe(CO)3 complexes (7-acyl) prepared by acylation of the mild organornetallic nucleophile (η3-C7H7)Fe(CO)3- isomerize readily to their 5-acyl and 6-acyl isomers. The 5-acyl isomer can be prepared in high yield by deprotonation of 7-acyl or 6-acyl followed by a proton quench. Refluxing 5- or 7-acyl in methanol gives the 6-acyl isomer. Rate studies have been carried out on the sequential isomerization of 7-acyl to 5-acyl to 6-acyl. Data were obtained by 1H NMR monitoring in methanol-d4 at 40°C. The results indicate that both steps of the isomerization involve an intermolecular proton-exchange mechanism. Solvent deprotonation of any of the three acyl isomers gives a common conjugate base that can be reprotonated at three sites. Kinetic protonation gives 5-acyl, and thermodynamic protonation gives 6-acyl. Mass spectral analysis shows small but significant amounts of multiple deuterium incorporation, suggesting that the common anion intermediate can also be protonated at the metal to give a transient iron hydride.
Regio- and stereocontrolled functionalization of a seven-membered ring via (cycloheptatriene)iron tricarbonyl
Williams,Rudisill,Barnum,Hardcastle,He yn,Kozak,McMillan
, p. 205 - 215 (2007/10/02)
Deprotonation of (cycloheptatriene)Fe(CO)3 gives a deep red nucleophilic anion (C7H7)Fe(CO)3(K+), 1. Anion 1 reacts with acid chlorides to give (7-exo-acyl-C7H7)Fe (CO)3/su
