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.
Intuitive Quantifiers of Charge Flows in Coordinate Bonding
Couzijn, Erik P. A.,Lai, Yu-Ying,Limacher, Armin,Chen, Peter
supporting information, p. 3205 - 3214 (2017/09/15)
ETS-NOCV charge and bond energy analyses have been carried out for a broad range of transition-metal carbonyl complexes L-[M], comprising different ligand classes, transition metals, and coordination geometries. The resulting electronic redistributions are visually assigned to σ donation, π backbonding, and related interactions. We propose a Hirshfeld partitioning of these electronic redistributions to afford the corresponding charge flow contributions Δqσ, Δqπ, etc. Taken together, a detailed picture of the dative bonding arises, in terms of both energetics and the extent of σ-electron donation and π-electron backbonding. The charge flows Δqσ and Δqπ appropriately quantify trends in the ligand σ-donor and π-acceptor abilities and are transferable across the transition-metal complexes studied and thus promise to be suitable descriptors for ligand knowledge bases. As a case in point, the TEP is well reproduced by the calculated νCO(A1) frequencies and is 3 times more strongly affected by Δqσ than by Δqπ, with an additional modest steric influence. Further, empirical relationships are derived among the charge flows Δqσ and Δqπ, the (L)W(CO)5 carbonyl stretching frequencies, and the ligand's steric volume %Vbur, which allow estimating the σ-donor and π-acceptor abilities of phosphines from experimental observables. On the other hand, direct Cl:→L-σ? interactions are identified in several cis-(L)Ir(CO)2Cl complexes, which compromises the use of these species as experimental probes for ligand parameters.
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.
Acrylic acid derivatives of group 8 metal carbonyls: A structural and kinetic study
Li, Bo,Kyran, Samuel J.,Yeung, Andrew D.,Bengali, Ashfaq A.,Darensbourg, Donald J.
, p. 5438 - 5447 (2013/06/26)
The synthesis, spectroscopic, and X-ray structural studies of acrylic acid complexes of iron and ruthenium tetracarbonyls are reported. In addition, the deprotonated η2-olefin bound acrylic acid derivative of iron as well as its alkylated species were fully characterized by X-ray crystallography. Kinetic data were determined for the replacement of acrylic acid, acrylate, and methylacrylate for the group 8 metal carbonyls by triphenylphosphine. These processes were found to be first-order in the concentration of metal complex with the rates for dissociative loss of the olefinic ligands from ruthenium being much faster than their iron analogues. However, the ruthenium derivatives afforded formation of primarily mono-phosphine metal tetracarbonyls, whereas the iron complexes led largely to trans-di-phosphine tricarbonyls. This difference in behavior was ascribed to a more stable spin crossover species 3Fe(CO)4 which undergoes rapid CO loss to afford the bis phosphine derivative. The activation enthalpies for dissociative loss of the deprotonated η2-bound acrylic acid ligand were found to be larger than their corresponding values in the protonated derivatives. For example, for dissociative loss of the protonated and deprotonated acrylic acid derivatives of iron(0) the ΔH? values determined were 28.0 ± 1.2 and 34.1 ± 1.5 kcal·mol-1, respectively. Density functional theory (DFT) computations of the bond dissociation energies (BDEs) in these acrylic acids and closely related complexes were in good agreement with enthalpies of activation for these ligand substitution reactions, supportive of a dissociative mechanism for olefin displacement. Processes related to catalytic production of acrylic acid from CO2 and ethylene are considered.
Reaction of ruthenium phenyl acetylide with iron-chalcogen clusters and iron pentacarbonyl
Mathur, Pradeep,Raghuvanshi, Abhinav,Ji, Radhe Shyam,Mobin, Shaikh M.
, p. 55 - 60 (2013/05/21)
Photolysis of a THF solution containing ruthenium acetylide [(η5-C5H5)Ru(PPh3) 2(η1-CCPh)] with [Fe3(CO) 9(μ3-Se)2] cluster affords an adduct [{μ-SeC(CpRu(PPh3)(CO))C(Ph)Se}(CO)6Fe2] (1), while under similar reaction condition with [Fe3(CO) 9(μ3-Te)2] cluster a Ru-inserted product [(η5-C5H5)(PPh3) (η1-CCPh)RuFe2(μ3-Te) 2(CO)6] (2) was obtained. Under thermal condition [(η5-C5H5)Ru(PPh3) 2(η1-CCPh)] react with Fe(CO)5 to give an acetylide stabilised Fe2Ru mixed metal cluster [(η5- C5H5)RuFe2(CO)7(η2: η2:η1-CCPh)], (3).
Phosphorus-carbon(pyridyl) bond cleavage on reacting diphenyl-2- pyridylphosphine with triiron dodecacarbonyl
Das, Pankaj,Borah, Malabika,Michaud, Francois,Petillon, Franois Y.,Schollhammer, Philippe
, p. 641 - 644 (2011/10/31)
The reaction of [Fe3(CO)12] with diphenyl-2- pyridylphosphine (PPh2Py) in refluxing toluene for 1 h afforded three compounds, [Fe2(CO)6(μ-PPh2)(μ- κ2-C,N-C5H4N)] (1), [Fe(CO) 4(κ1-P-PPh2Py)] (2), and [Fe(CO) 3(κ1-P-PPh2Py)2] (3) in 23%, 10% and 3.5% yields after work-up, respectively. The PPh2Py ligand acts as a terminal P-donor ligand in 2 and 3, while in 1 it underwent a selective phosphorus-carbon(pyridyl) bond cleavage to afford phosphido- and pyridyl-bridged ligands. The complexes were characterized by elemental analysis, FAB-mass, FTIR, 1H and 31P-{1H}NMR spectroscopies. Compounds 1 and 2 were also characterized by X-ray single crystal.
Chemistry of vinylidene complexes. XX. Intramolecular carbonylation of vinylidene on the MnFe center: Spectroscopic and structural study. X-ray structure of the new trimethylenemethane type MnFe complex
Antonova, Alla B.,Chudin, Oleg S.,Vasiliev, Alexander D.,Rubaylo, Anatoly I.,Verpekin, Victor V.,Sokolenko, William A.,Pavlenko, Nina I.,Semeikin, Oleg V.
, p. 963 - 970 (2011/03/21)
Reactions of Fe2(CO)9 with Cp(CO)2MnCCHPh (1) and Cp(CO)(PPh3)MnCCHPh (3) gave the heterometallic trimethylenemethane complexes η4-{C[Mn(CO)2Cp](CO) CHPh}Fe(CO)3 (2) and η4-{C[Mn(CO)(PPh 3)Cp](CO)CHPh}Fe(CO)3 (4), respectively. The formation of the benzylideneketene [PhHCCCO] fragment included in complexes 2 and 4 occurs via intramolecular coupling of the carbonyl and vinylidene ligands. The structures of 3 and 4 were determined by single crystal XRD methods. The influence of the nature of the L ligands at the Mn atom on the structural and spectroscopic characteristics of η4-{C[Mn(CO)(L)Cp](CO)CHPh} Fe(CO)3 (L = CO (2), PPh3 (4)) is considered. According to the VT 1H and 13C NMR spectra, complex 2 reversibly transforms in solution into μ-η1:η1-vinylidene isomer Cp(CO)2MnFe(μ-CCHPh)(CO)4 (2a), whereas complex 4 containing the PPh3 ligand is not able to a similar transformation.
Phosphine addition to pyruvoyl ligands of iron complexes: Formation of zwitterionic metallalactones
Salauen,Rumin,Setifi,Triki,Jaffres
, p. 216 - 224 (2009/05/30)
Tertiary phosphines react, at -80 °C, with the pyruvoyl-substituted iron complex (CO)4Fe[C(O)C(O)CH3](CO2CH 3) (1) to give rise to phosphonium-substituted metallalactones fac-(CO)3e[C(O)C(CH3/su
Proton sponge phosphines: Electrospray-active ligands
Farrer, Nicola J.,McDonald, Robert,McIndoe, J. Scott
, p. 4570 - 4579 (2007/10/03)
Attachment of a proton sponge to a phosphine ligand renders neutral complexes of the ligand highly amenable to analysis by electrospray ionisation mass spectrometry (ESI-MS). The ligand 1,8-bis(dimethylamino) naphthyldiphenylphosphine (3) is extremely eff
