79795-91-8

Upstream product

• 21050-13-5 bis(triphenylphosphine)iminium chloride 

Downstream Products

• 98705-17-0 ((C₆H₅)3P)2N⁽¹⁺⁾*Fe₄(C(CH₂COOCH₃)CHCCOOCH₃)(CO)11^(1-)=((C₆H₅)3P)2N(Fe₄(C(CH₂COOCH₃)CHCCOOCH₃)(CO)11) 
• 98705-13-6 ((C₆H₅)3P)2N⁽¹⁺⁾*Fe₄(C(CH₃)CHCH)(CO)11^(1-)=((C₆H₅)3P)2N(Fe₄(C(CH₃)CHCH)(CO)11) 
• 98705-19-2 ((C₆H₅)3P)2N⁽¹⁺⁾*Fe₃(CCC(CH₃)3)(CO)9^(1-)=((C₆H₅)3P)2N(Fe₃(CCC(CH₃)3)(CO)9) 
• 98705-21-6 ((C₆H₅)3P)2N⁽¹⁺⁾*Fe₃(CC(CH₂)2CH₃)(CO)9^(1-)=((C₆H₅)3P)2N(Fe₃(CC(CH₂)2CH₃)(CO)9) 

Relevant academic research and scientific papers

NMR spectroscopic characterization of the two isomers of [HFe4(CO)13]-

Low-temperature 13C and 1H NMR spectra of [HFe4(CO)13]- demonstrate the presence of two distinct hydride species which are in equilibrium at room temperature. One of these displays a 1H NMR resonance at -24.9 ppm and is assigned to a butterfly geometry for the Fe4 framework while the other has a 1H resonance at -16.9 ppm and appears to be due to a closed Fe4 tetrahedron. Both species begin to equilibrate at approximately -30°C. The low-temperature, -80°C, 13C NMR spectrum of the species which is assigned the butterfly geometry is in full accord with the previously determined X-ray structure. The proposed tetrahedral isomer of [HFe4(CO)13]- displays a single 13C resonance at 216.7 ppm, indicating rapid fluxional behavior down to the lowest temperatures studied (-80°C). 17O NMR spectra were obtained, but they do not provide further insight into the nature of the two isomers.

Study of the reactivity of [HFe4(CO)13]- toward acetylene and monosubstituted alkynes. X-ray structure determination of [N(P(C6H5)3)2][Fe 4(μ4-η3-C(CH 3)CHCH)(μ-CO)2(CO)9]

[PPN][HFe4(CO)13] (1; PPN = N(P(C6H5)3)2) reacts with acetylene in boiling ethyl acetate to give [PPN][Fe4(μ3-CCH3)(CO)12] (2) in a first step. This cluster then reacts with a second molecule of acetylene in boiling 3-pentanone leading to [PPN][Fe4(μ4-η3-C(CH 3)CHCH)(μ-CO)2(CO)9] (3) whose structure has been determined by X-ray diffraction. 3 is monoclinic of space group C2h5-P21/n with a = 23.014 (4) A?, b = 9.420 (1) A?, c = 22.166 (4) A?, β = 90.45 (1)°, and Z = 4. The structure has been solved and refined to R and Rw values of 0.026 and 0.030, respectively, using 4539 reflections. 3 contains an allylic ligand, resulting from the coupling of the ethylidyne ligand with one molecule of acetylene, μ4-η3-bonded to a butterfly arrangement of the four iron atoms. Extension of the study to monosubstituted alkynes, RC≡CH, shows that the reaction is alkyne dependent and two types of reactions have been observed. If the substituents on the alkyne have electron-withdrawing properties like R = C6H5 or CH3OC(O), complexes of type 3 with the C(CH2R)CHC(R) allylic ligand are formed directly without observation of the alkylidyne intermediate. If the substituents R are electron-donating alkyl groups, fragmentation of the tetranuclear unit of the cluster is observed and trinuclear anionic clusters [PPN][Fe3(μ3-C≡CR)(CO)9] are formed. The fluxionality of complexes with the structure of 3 is also discussed.