35679-07-3Relevant articles and documents
Trinuclear ReFePt clusters with a μ3-phenylvinylidene ligand: synthetic approaches, rearrangement of vinylidene, and redox-induced transformations
Burmakina, Galina V.,Chudin, Oleg S.,Kondrasenko, Alexander A.,Maksimov, Nikolai G.,Rubaylo, Anatoly I.,Shor, Aleksey M.,Vasiliev, Alexander D.,Verpekin, Victor V.,Zimonin, Dmitry V.
supporting information, p. 324 - 339 (2021/12/27)
A series of trinuclear μ3-vinylidene ReFePt clusters were synthesized by the application of two approaches: (i) reactions of the binuclear RePt μ-vinylidene complexes with Fe2(CO)9; (ii) ligand substitution or exchange reactions at the Pt atom in the synthesized ReFePt clusters. The molecular structures of CpReFePt(μ3-CCHPh)(CO)5[P(OEt)3]L [L = CO; P(OEt)3] were determined by an X-ray diffraction study. The obtained compounds were studied by IR and1H,13C and31P NMR spectroscopy. The spectroscopic study revealed that the clusters CpReFePt(μ3-CCHPh)(CO)5[P(OEt)3]L [L = CO; P(OEt)3] and CpReFePt(μ3-CCHPh)(CO)6[P(OPri)3] undergo isomerization upon dissolution, resulting in three isomers with different positions of the μ3-vinylidene ligand over the ReFePt core. The redox properties of the clusters were studied by electrochemical methods. The relatively stable cation-radicals obtained by chemical oxidation of CpReFePt(μ3-CCHPh)(CO)6[P(OPri)3] and CpReFePt(μ3-CCHPh)(CO)5[P(OEt)3]2with ferrocenium tetrafluoroborate were characterized by EPR spectroscopy.
Iron pentacarbonyl in alkoxy- and aminocarbonylation of aromatic halides
Babjak, Matej,Caletková, O?ga,?uri?ová, Diana,Gracza, Tibor
supporting information, p. 2579 - 2584 (2015/01/09)
We have identified reaction conditions for a Heck-type carbonylation based on [Fe(CO)5]. Preliminary optimization of alkoxycarbonylation on 2-bromonaphthalene defined functioning composition of the reaction mixture which was then applied on a small set of (hetero)aromatic halides. Respective aminocarbonylation of these halides with different amines, including aniline and benzotriazole, was accomplished with reasonable results.
Light-enhanced displacement of methyl acrylate from iron carbonyl: Investigation of the reactive intermediate via rapid-scan fourier transform infrared and computational studies
Muhammad, Sohail,Moncho, Salvador,Li, Bo,Kyran, Samuel J.,Brothers, Edward N.,Darensbourg, Donald J.,Bengali, Ashfaq A.
, p. 12655 - 12660 (2013/11/19)
The thermal displacement of methyl acrylate from Fe(CO)4(η 2-CH2=CHCOOMe) by phosphine ligands is a relatively slow reaction requiring several hours at elevated temperatures. In the present study, it is observed that photolysis of the tetracarbonyl complex with UV light activates the process such that the reaction is complete within a few seconds. This rate enhancement is due to the formation of an intermediate η4 complex where the organic C=O and C=C units of methyl acrylate occupy axial and equatorial coordination sites on the Fe center, respectively, following photochemical CO loss. The displacement of methyl acrylate from this photolytically generated intermediate is facile with a remarkably low barrier of 8.7 kcal/mol. Density functional theory calculations support these experimental observations.
