12110-44-0Relevant academic research and scientific papers
Synthesis of diiron μ-allenyl complexes by electrophilic addition to propen-2-yl-dimetallacyclopentenone species: A joint experimental and DFT study
Agonigi, Gabriele,Bortoluzzi, Marco,Funaioli, Tiziana,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
, p. 61 - 66 (2013)
The propen-2-yl-dimetallacyclopentenone complex [Fe2Cp 2(CO)(μ-CO){μ-η1:η3-C α(H)Cβ(Cγ(CH 3)CH2)C(O)}] (1) underwent electrophilic additions at the propenyl moiety to afford the μ-allenyl complexes [Fe2Cp 2(CO)2(μ-CO){μ-η1: η2α,β-CαHC βCγ(CH3)(CH2E)}][BF 4] (E = CPh3, [2][BF4]; E = H, [3][BF 4]), in ca. 85% yield. The molecular structure of ([2][BF 4]) was ascertained by X-ray diffractometry; X-ray, NMR and DFT results agreed in that one single isomer formed, bearing the [CH 2CPh3] group pointing far from the Fe-Fe axis. The reaction of [3][BF4] with NHEt2 in the presence of PhSSPh resulted in the prevalent formation of [FeCp(CO)2SPh] (7).
Synthesis and structure of heterobimetallic compounds with a single thiolato-bridged ligand
Hossain, Md. Munkir,Lin, Hsiu-Mei,Shyu, Shin-Guang
, p. 2655 - 2659 (2007/10/03)
Reactions between CpFe(CO)2SPh and M(CO)5THF (M = Cr, Mo, and W) in a mixture of benzene and THF at room temperature afforded compounds of the type CpFe(CO)2(μ-SPh)M(CO)5 (1) [M = Cr (1a), Mo (1b), and W (1c)] in high yield. However, migration of the thiolato ligand occurred during reactions between CpM(CO)xSPh (M = Fe, x = 2; M = Mo and W, x = 3) and Fe2(CO)9 forming compounds [Fe(μ-SPh)(CO)3]2 and [CpM(CO)x]2 (M = Fe, x = 2; M = Mo and W, x = 3). Single-crystal X-ray diffraction analyses reveal that 1c is a single thiolato-bridged hererobimetallic compound without a metal-metal bond. Metal-metal bond formation in compounds 1 by decarbonylation under thermal or photolytic condition was not observed. Reactions between compounds 1 and PPh3 produced CpFe(CO)2SPh and PPh3M(CO)5 (M = Cr, Mo, and W) by M-S bond cleavage in 1.
REACTIVITIES OF LEWIS ACID ADDUCTS OF η5-C5H5(FeCO)2Y (Y=SPh, SO2Ph, AND PPh2) WITH NUCLEOPHILES
Weers, Jerry J.,Eyman, Darrell P.
, p. 47 - 55 (2007/10/02)
Complexes of the type CpFe(CO)2Y (Cp=η5-C5H5, Y=SPh(I), Y=PPh2 (II), Y=SO2Ph (III) and Cp'Fe(CO)2SPh (Cp'=η5-C5(CH3)5 (IV)), form adducts with the Lewis acids AlMe3, AlMe2Cl or AlBr3.All of the Lewis acid adducts of I react with one
REACTIONS OF SOME IRON AND TUNGSTEN MERCAPTO-COMPLEXES WITH ELECTROPHILIC ACETYLENES LEADING TO NOVEL METALLACYCLES. THE CRYSTAL AND MOLECULAR STRUCTURE OF η2-VINYL COMPLEX 2-C(CF3)C(CF3)-C(O)SMe>(CO)2(η5-C5H5)>
Davidson, Jack L.,Shiralian, Mahmoud,Manojlovic-Muir, Ljubica,Muir, Kenneth W.
, p. 2167 - 2176 (2007/10/02)
Reactions of 5-C5H5)> with activated alkynes CF3CCCF3 and MeO2CCCCO2Me give heterocyclic complexes (R' = alkyl or aryl, R = CF3 or CO2Me).Related derivatives (R' = Me or Et) obtained from 5-C5H5)> and the alkynes in hexane at 20 deg C undergo a sequence of thermal isomerisations above 25 deg C involving initially a novel 1,3 shift of the SR' ligand across the eneone ligand to give the η2-vinyl complex 2-C(R)C(R)C(O)SR'>(CO)2(η5-C5H5)> (R = CF3 only) followed by S-bonded vinyl ketone complexes and ultimately O-bonded vinyl ketone derivatives and co-ordinatively unsaturated alkyne complexes CR)(η5-C5H5)> (R = CF3 only).An X-ray structure determination of the η2 -vinyl complex 2-C(CF3)C(CF3)C(O)SMe>(CO)2(η5-C5H5)> reveals the first example of a vinyl group bonded to a metal via both carbon atoms and therefore acting as a three-electron donor ligand.The structure consists of an approximately octahedrally co-ordinated tungsten atom bonded to an η5-C5H5 ligand which occupies one face of the octahedron.Two carbonyl ligands occupy two octahedral sites while the third is occupied by the Η2-C(CF3)C(CF3)C(O)SMe ligand which adopts an orientation such that the vinylic C-C axis lies approximately parallel to one of the W-CO axes.
Oxidative coupling of mercaptide ligands in organometallic thiolate complexes
Treichel, Paul M.,Rosenhein, Laurence D.,Schmidt, Mark S.
, p. 3960 - 3965 (2008/10/08)
The one-electron oxidations of Fe(SPh)(CO)2(η-C5R5) by NOPF6 (R = Me, H) or AgPF6 (R = Me) produce diamagnetic complexes having the general formula [(η-C5R5)(CO)2Fe(μ-PhSSPh)Fe(CO) 2(η-C5R5)](PF6)2. The route to these complexes, which have bridging diphenyl disulfide ligands, probably involves loss of a nonbonding electron from the mercaptide ligand followed by coupling of the resulting ligand-centered radical species. The BF4- salt of the cyclopentadienyl complex may also be obtained by a reaction of [Fe(THF)(CO)2(η-C5H5)]BF4 and PhSSPh in a 2:1 ratio. Complexes with monodentate disulfide ligands, [Fe(RSSR)(CO)2(η-C5H5)]BF4 (R = Me, Ph), are obtained from 1:1 reactions of the disulfide and [Fe(THF)(CO)2(η-C5H5)]BF4. Oxidations of several monosubstituted Fe(SPh)(CO)(L)(η-C5R5) compounds (R = H, Me; L = PPhMe2, PPh2Me, PMe3, P(OPh)3, P(OEt)3) and two disubstituted compounds Fe(SPh)(CNR)2(η-C5H5) (R = m-C6H4OMe, m-C6H4CF3) produce dark solids having stoichiometries [Fe(SPh)(CO)(L)(η-C5H5)]PF6 and [Fe(SPh)(CNR)2(η-C5H5)]BF4. These compounds, as solids, have magnetic moments between 0.5 and 2.3 μB. Their behavior in solution is consistent with the existence of an equilibrium between paramagnetic and diamagnetic dimers. Oxidation of another disubstituted species, Fe(SPh)(P(OPh)3)2(η-C5H5), produces [Fe(SPh)(P(OPh)3)2(η-C5H 5)]PF6, a typical low-spin iron(III) complex; this is similar to results observed previously with disubstituted phosphine complexes, Fe(SPh)(L)2(η-C5H5) (L = PMe3, L2 = dppe).
