A5011313760- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Ferrocene Chemistry and Applications
- Molecular Junctions and Nanostructures
- Organometallic Complex Synthesis and Catalysis
- Crystallography and molecular interactions
- Silicone and Siloxane Chemistry
- Organoboron and organosilicon chemistry
- Synthesis and characterization of novel inorganic/organometallic compounds
- Conducting polymers and applications
- Sulfur-Based Synthesis Techniques
- Molecular Sensors and Ion Detection
- Magnetism in coordination complexes
- Metal complexes synthesis and properties
- Synthetic Organic Chemistry Methods
- Dendrimers and Hyperbranched Polymers
- Carbon dioxide utilization in catalysis
- Organic Electronics and Photovoltaics
- Quantum Mechanics and Applications
- Metalloenzymes and iron-sulfur proteins
- Click Chemistry and Applications
- stochastic dynamics and bifurcation
- Inorganic and Organometallic Chemistry
- Protein Interaction Studies and Fluorescence Analysis
- Marine Biology and Environmental Chemistry
Universidad Autónoma de Madrid
2012-2024
University of Strathclyde
2020
University of Genoa
1999-2002
The potential of structurally new ferrocene-functionalized guanidines as redox-active precursors for the synthesis heterometallic platinum(II)–guanidine complexes with anticancer activity was studied. To this end, an atom-economical catalytic approach followed by using ZnEt2 to catalyze addition aminoferrocene and 4-ferrocenylaniline N,N′-diisopropylcarbodiimide. Furthermore, reaction a platinum(II) source newly obtained Fc–N═C(NHiPr)2 (3) Fc(1,4-C6H4)–N═C(NHiPr)2 (4) provided access...
A new family of heterometallic compounds 3-6 containing ferrocenyl and platinum(II) centers has been synthesized by reaction 1-β-aminoethylferrocene (1) 1,1'-bis(β-aminoethyl)ferrocene (2) with Pt(II) precursors. Using K(2)[PtCl(4)] as the source, cis-square-planar neutral [Fe{η(5)-C(5)H(4)(CH(2))(2)NH(2)}(2)PtCl(2)] (3) [{Fe(η(5)-C(5)H(4)(CH(2))(2)NH(2))(η(5)-C(5)H(5))}(2)PtCl(2)] (5) were obtained. Reaction cis-[PtCl(2)(dmso)(2)] 1 2 resulted in displacement dmso chloride ligands from...
Novel highly functionalized polysiloxanes have been synthesized, which bear small pendant dendritic wedges containing two different redox-active organometallic moieties, namely the electron-donating ferrocenyl group and electron withdrawing (η6-aryl)tricarbonylchromium entity. Hydrosilylations of vinylsilyl-functionalized (CH2═CH)MePhSiFc (1) allylsilyl-terminated dendron (CH2═CHCH2)PhSi[(CH2)2MePhSiFc]2 (3), with Si–H-containing polysiloxane backbones (Me3SiO)(MeSiHO)n(Me2SiO)m(SiMe3) (n =...
The potential of vinylferrocene Fc(CH═CH2) (1) as redox-active ene functional precursor for thiol–ene radical reaction has been successfully investigated the first time. To this end, we initially studied model reactions 1 with a variety functionalized monothiols, including 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic acid, (3-mercaptopropyl)trimethoxysilane, 2-aminoethanethiol hydrochloride, dithiol 2,2′-(ethylenedioxy)diethanethiol, and tetrafunctional thiol pentaerythritol...
The construction of the first members a novel family structurally well-defined, ferrocenyl rich, dendritic macromolecules based on carbosilane skeletons and siloxane linkages has been achieved via convergent growth approach. Starting from triferrocenylvinylsilane Fc3SiCHCH2 (1) (Fc = Fe(η5-C5H4)(η5-C5H5) as key monomer, sequential utilization platinum-catalyzed hydrosilylation alkenylation steps with Grignard reagents (allylmagnesium bromide) can be applied to prepare three different...
A new series of vinyl-functionalized polyferrocenyl organosilicon compounds, including triferrocenylvinylsilane, (CH2═CH)Si(Fc)3 (7) (Fc = (η5-C5H4)Fe(η5-C5H5)), 1,3-divinyl-1,1,3,3-tetraferrocenyldisiloxane, [(CH2═CH)(Fc)2Si]2O (8), and 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane, [(CH2═CH)(Fc)MeSi]2O (9), have been synthesized via the low-temperature salt metathesis reaction monolithioferrocene chlorosilanes (CH2═CH)SiCl3 [(CH2═CH)(Cl)MeSi]2O. Compounds 7−9 were characterized by...
A series of novel, precisely defined, redox-active macrocyclic and linear co-oligocarbosiloxanes containing pendant ferrocenyl moieties attached to the carbosiloxane backbones, have been synthesized via hydrosilylation reactions bifunctional 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane [(CH2═CH)(Fc)MeSi]2O (6) (Fc = (η5-C5H4)Fe(η5-C5H5)). Specifically, 6 was reacted with 1,1,3,3-tetramethyldisiloxane, in presence Karstedt's catalyst, afford both cyclic species 7, 8 9n (n 3–6) several...
Redox-active, highly symmetrical cubic octasilsesquioxanes (OS) peripherally decorated with 24 ferrocenyl units, linked in threes around the periphery of a cage, namely, [Fc3Si(CH2)2Me2SiO]8Si8O12 (6) and [Fc3Si(CH2)2]8Si8O12 (7) (Fc = (η5-C5H4)Fe(η5-C5H5)), have been synthesized. Such integrally ferrocenyl-functionalized macromolecules 6 7, as well related small-molecule models hexaferrocenyldisiloxane [Fc3Si(CH2)2Me2Si]2O (4) dodecaferrocenyl cyclotetrasiloxane [Fc3Si(CH2)2MeSiO]4 (5),...
A new heterometallic electroactive compound having the ferrocenyl moiety attached to platinum atom through an amidine functionality has been prepared viaPt(II)-mediated nucleophilic addition of β-aminoethylferrocene a benzonitrile ligand. This neutral receptor shows remarkable electrochemical anion-sensing redox response H2PO4−.
The application of ethynylferrocene, FcC≡CH (1), as a highly efficient electroactive precursor for the thiol–yne click reaction is presented. For this purpose, wide range functionalized thiols, namely 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic acid, 4-aminothiophenol, and benzene-1,3-dithiol well tetrathiol pentaerythritol tetrakis(3-mercaptopropionate), were investigated. This facile thiol–ethynylferrocene radical has resulted in quantitative formation isolation newly...
The binding interactions between a novel ferrocenylguanidinium derivative (FcG+) and the macrocyclic hosts cucurbit[7]uril (CB7) cucurbit[8]uril (CB8) were investigated in aqueous solution. 1H NMR spectroscopic experiments indicated that both form stable 1:1 inclusion complexes with FcG+, which ferrocenyl group is engulfed by host cavity. stoichiometry of CB7·FcG+ complex was also confirmed electrospray mass spectrometric (ESI MS) experiments. association equilibrium constants (K) determined...
The ability of diferrocenylsilanediol, Fc2Si(OH)2 (5), and 1,1,3,3-tetraferrocenyldisiloxane-1,3-diol, Fc2(HO)Si–O–Si(OH)Fc2 (6), to act as new electroactive anion receptors for either acetate or chloride anions has been investigated in solution, the solid state, gas phase. 1H NMR spectroscopic titrations with reveal that binding interaction causes chemical-shift perturbations not only Si–OH hydrogen-bonding donor motif but also ferrocenyl protons 5 6. Square-wave voltammetric studies...
The application of 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane [(CH2═CH)FcMeSi]2O (1) as an efficient electroactive vinylsilane precursor for thiol–ene radical reactions is described. In order to determine if steric or electronic limitations due the redox-active metallocene moiety might affect bis(hydrothiolation) bifunctional vinylsilane, a model reaction was initially performed between 1 and 2-mercaptoethanol, resulting in formation newly sulfur-containing carbosiloxane 2 excellent...
Redox-responsive polysulfide materials, synthesized via inverse vulcanization, exhibit a synergistic ferrocene–sulfur effect, evidenced by their ability to electrochemically detect environmental hazardous Hg 2+ and Cd cations.
Simple manual grinding of solid cyanomethylferrrocene (1) and silica gel provides a facile one-pot access route to prepare unexpected highly electron-poor metallocene, 1-cyanocarbonylferrocene (2). Electrochemical measurements supported by computational studies reveal that 2 exhibits the highest FeII/FeIII oxidation potential reported for mono-substituted ferrocenes.
Reaction of Fe3(CO)12 with 1,2-dithiolene HSC6H2Cl2SH affords a mixture complexes [Fe2(CO)6(μ-SC6H2Cl2S)] 1, [Fe2(SC6H2Cl2S)4] 2 and [Fe3(CO)7(μ3-SC6H2Cl2S)2] 3. In the course reaction trimetallic cluster 3 is first formed then converted into known dinuclear compound 1 to afford finally neutral diiron tetrakis(dithiolato) derivative 2. Compounds have been studied by Mössbauer spectroscopy, X-ray crystallography theoretical calculations. metal atoms are in an intermediate-spin Fe(III) state...
Novel vinylferrocenyl-functionalized cyclic and linear polysiloxanes [MeSi{C(Fc)═CH2}O]4 (1) (Me3SiO)(MeSi{C(Fc)═CH2}O)n(SiMe3) (n ≈ 35) (3) (Fc = (η5-C5H4)Fe(η5-C5H5) have been synthesized by hydrosilylation reactions of the heterometallic compound Co2(CO)6(μ,η2-HCCFc) with Si–H-functionalized polysiloxane frameworks [MeSiHO]4 (Me3SiO)(MeSiHO)n(SiMe3). The solution electrochemical behavior 1 3 has investigated showed that all vinylferrocenyl units present in molecules are electrochemically...
The formation of a family silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc2(CH3)3C(CH2)2SiCH[double bond, length as m-dash]CH2 (5), Fc2(CH2[double m-dash]CH-O)SiCH[double (6), Fc2(OH)SiCH[double (7), m-dash]CH-O)Si-O-Si(O-CH[double m-dash]CH2)Fc2 (8) m-dash]CH-O)Si-O-SiFc3 (9) is described. Silyl vinyl ether molecules 6, 8 9 the heteroleptic vinylsilane 5 resulted from competing metathesis reaction...
The thiol-yne coupling chemistry of diferrocenylacetylene (FcCCFc) 1, bearing two electron rich and redox-active ferrocenyl units (Fc = Fe(η5-C5H4)(η5-C5H5)) an internal triple bond, has been investigated for the first time. In order to determine whether steric limitations might affect hydrothiolation, a model reaction using functionalized monothiol was tested, namely 2-mercaptoethanol I. thiol-diferrocenylacetylene reactions were initiated either thermally (in toluene with AIBN) or by UV...
The titanium complex [TiCp*(thiosal)(thiosalH)] (1) has been synthesised by reaction of [TiCp*Me3], Cp* = η5-C5Me5, with thiosalicylic acid (H2thiosal). Complex 1 reacts [M(μ-OH)(COD)]2 (M Rh, Ir) to yield the corresponding early-late heterobimetallic complexes [TiCp*(thiosal)2M(COD)] Rh (2); Ir (3)). Carbon monoxide replaces COD ligand in 2 and 3 leading respective dicarbonyl [TiCp*(thiosal)2M(CO)2] (4); (5)). Compound 4 PPh3 monocarbonyl derivative [TiCp*(thiosal)2Rh(CO)(PPh3)] (6)....
Abstract The Grignard reagent, i PrMgCl and its lithium chloride‐enhanced ‘turbo’ derivative PrMgCl⋅LiCl have been employed to investigate the single iodo/magnesium exchange reactions of trisubstituted arenes, 2,5‐diiodo‐ N , ‐diisopropylbenzamide 1 1,4‐diiodo‐2‐methoxybenzene 2 1,4‐diiodo‐2‐(trifluoromethyl)benzene 3 . These three arenes themselves were initially prepared by a double ortho‐, meta ′‐deprotonation ‐diisopropylbenzamide, anisole (trifluoromethyl)benzene, respectively, using...