1291-31-2Relevant academic research and scientific papers
(Electrochemical) Properties and Computational Investigations of Ferrocenyl-substituted Fe3(μ3-PFc)2(CO)9 and Co4(μ4-PFc)2(CO)9 Clusters and Their Reduced Species
Dmitrieva, Evgenia,Korb, Marcus,Lang, Heinrich,Liu, Xianming,Popov, Alexey A.,Rosenkranz, Marco,Walz, Sebastian
, (2020)
The formation of ferrocenyl-functionalized iron and cobalt carbonyl clusters is reported, based on a reaction of FcPCl2 (3) (Fc = Fe(ν5-C5H5)(ν5-C5H4)) with Fe2(CO)9 and Co2(CO)8, respectively. Therein, nido-Fe3(CO)9(μ3-PFc)2 (4) and nido-Co4(CO)10(μ3-PFc)2 (5) clusters were obtained as the first diferrocenyl-substituted carbonyl clusters with a symmetrical cluster core. Cluster 4 shows two reversible one-electron processes within the anodic region, based on Fc/Fc+ redox events, as well as two processes in the cathodic region. In situ IR and electron paramagnetic resonance (EPR) measurements of all electronic states confirmed an Fc-based oxidation and a core-based reduction. On the basis of the results of a single-crystal X-ray analysis of structures of 4 and 5, computational studies of the highest occupied molecular orbital-lowest unoccupied molecular orbital energies, the spin density, quantum theory of atom-in-molecule delocalization indices, and the atomic charges were performed to explain the experimental results. The latter revealed a reorganization of the cluster core upon reduction and the existence of weak P···P interactions in 4 and 5. Ferrocenyl-related redox processes, occurring reversibly in case of 4, were absent for 5, due to a different distribution of the HOMO energies. EPR measurements furthermore confirmed the core-based radical anion and the formation of a decomposition product at potentials lower than [M]2- (M = Fe, Co).
Ferrocene derivatives. 27. Ferrocenyldimethylphosphine
Knox, Graham R.,Pauson, Peter L.,Willison, Debra
, p. 2930 - 2933 (1992)
An improved synthesis of ferrocenyldimethylphosphine, FcPMe2, is limited only by the unreliable literature procedure for preparing precursor dichloroferrocenylphosphine, FcPCl2. The latter compound yields a crystalline copper(I) iodide complex on reaction with lithium dimethylcuprate. Methanolysis of FcPCl2 yields unstable dimethyl ferrocenylphosphonite, FcP(OMe)2. which is converted to methyl ferrocenylphosphinite, FcPH(O)OMe, on heating or chromatography.
An efficient, scalable synthesis of ferrocenylphosphine and dichloroferrocenylphosphine
Surgenor, Brian A.,Taylor, Laurence J.,Nordheider, Andreas,Slawin, Alexandra M. Z.,Athukorala Arachchige, Kasun S.,Woollins, J. Derek,Kilian, Petr
, p. 5973 - 5976 (2016)
A new synthetic route to FcPH2 and FcPCl2 (Fc = ferrocenyl) is presented. This method avoids the challenging monolithiation of ferrocene, as well as any tedious purification steps. All reactions are high yielding and easily conducted on a relatively large scale, using economical and commercially available synthetic precursors.
Structural Variety of Iron Carbonyl Clusters Featuring Ferrocenylphosphines
Korb, Marcus,Liu, Xianming,Walz, Sebastian,Mahrholdt, Julia,Popov, Alexey A.,Lang, Heinrich
supporting information, p. 2017 - 2033 (2021/05/18)
The reaction chemistry of Fe2(CO)9 (10) with ferrocenenyl dichlorophosphines of different substitution is discussed. Single FcPCl2, (5) as well as 1,1’- (6) and 1,2- (9) difunctionalized phosphines were used, of which 6 and 9, were prepared in a novel straightforward synthetic process. Substrate 5 gave butterfly-shaped Fe2(CO)6(μ2-Cl)(μ2-PFcCl) and Fe2(CO)6(μ2-PFcR1)(μ2-PFcR2) (R1, R2=Cl, H). In addition, nido-Fe3(CO)10(μ3-PFc) and nido-Fe3(CO)9(μ3-PFc)2 were obtained. 1,1’-Functionalized 6 bridges both ends of the Fe2(CO)6 entity. Therein, the so far smallest non-binding P???P distance (2.7674(12) ?) between both 1,1’-substituents is observed. Additionally, an ‘organometallic octabisvalene’, containing two [2]ferrocenophane entities was obtained. The eight-membered cyclic structure is twisted by 35.31(9)° regarding their ferrocenyl axis. Usage of 1,2-(PCl2)2 functionalized 9 produced two isomers of a P?P connected dimer, which coordinates towards two independent Fe2(CO)6 fragments in a novel μ,μ’,κ8 or bis(μ,κ4) fashion, resulting in a meso isomer with a planar core, and a racem mixture, possessing a pocket-type structure. The latter shows the so far shortest observed P???P distance of 2.950(7) ? between two ortho P atoms of a ferrocenyl backbone. The results confirm that the geometric properties of ferrocenyls featuring 1,1’- and 1,2-substitution patterns are not comparable with phenyl-based analogues. X-ray single crystal solid state structures, and DFT calculations were carried out.
Synthesis and characterisation of four- and six-membered P-Se heterocycles
Parveen, Sahrah,Kilian, Petr,Slawin, Alexandra M. Z.,Woollins, J. Derek
, p. 2586 - 2590 (2007/10/03)
The preparation, spectroscopic characterisation and crystal structures of [FcP(-Se)Se]2, [FcP(-Se2)Se]2 and [PhP(-Se 2)Se]2 are reported. Crystallographic data reveal planar four-membered PSePSe and skewed six-membered P2Se4 rings, respectively, in all cases with trans arrangement of organic substituents and exo selenium atoms. Whilst stable at room temperature in solid state, NMR data suggest the six-membered rings of both the ferrocenyl and phenyl compounds decompose in the solution with loss of red selenium, forming PSe2PSe five-membered rings. The Royal Society of Chemistry 2006.
METALLOCENEPHOSPHORAMIDES, 2. AMIDES OF FERROCENEPHOSPHONOUS AND FERROCENEDIPHOSPHONOUS ACIDS
Nifant'ev, I. E.,Boricenko, A. A.,Manzhukova, L. F.,Nifant'ev, E. E.
, p. 99 - 106 (2007/10/02)
The first examples of phosphorylated metallocenes containing P(III)-N bond were prepared.Two synthetic routes were developed: treating iron(II)bromide with phosphorylated sodium cyclopentadienide and the reaction of mono- and dilithiated ferrocenes with chlorides of diamidophosphorous acids.Two heterocyclic amides were obtained via chlorides of ferrocenediphosphonous acid. Key words: Ferrocene; phosphoramides
