A convergent growth approach to electroactive ferrocene rich carbosilane- and siloxane-based dendrons, dendrimers, and dendronized polymers.

The construction of the first members of a novel family of structurally well-defined, ferrocenyl rich, dendritic macromolecules based on carbosilane skeletons and siloxane linkages has been achieved a convergent growth approach. Starting from triferrocenylvinylsilane FcSiCHCH (1) (Fc = Fe(η-CH)(η-CH) as the key monomer, the sequential utilization of platinum-catalyzed hydrosilylation and alkenylation steps with Grignard reagents (allylmagnesium bromide) can be applied to prepare three different branched structures: multiferrocenyl-terminated dendrons 2 and 3, dendrimers 4 and 5, and dendronized polymers 7n-9n. All of the dendritic metallomacromolecules have been thoroughly characterized using a combination of elemental analysis, multinuclear (H, C, Si) NMR spectroscopy, FT-IR and MALDI-TOF mass spectrometry, to establish their chemical structures and properties.

Thiol-yne chemistry of diferrocenylacetylene: from synthesis and electrochemistry to theoretical studies.

The thiol-yne coupling chemistry of diferrocenylacetylene (FcCCFc) 1, bearing two electron rich and redox-active ferrocenyl units (Fc = Fe(η-CH)(η-CH)) and 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 a functionalized monothiol was tested, namely 2-mercaptoethanol I. The thiol-diferrocenylacetylene reactions were initiated either thermally (in toluene with AIBN) or by UV light irradiation (in THF and in the presence of DMPA as the photoinitiator).

Titanium thiosalicylate complexes: functional metalloligands for the construction of redox-active heterometallic architectures.

The titanium complex [TiCp*(thiosal)(thiosalH)] (1) has been synthesised by reaction of [TiCp*Me], Cp* = η-CMe, with thiosalicylic acid (Hthiosal). Complex 1 reacts with [M(μ-OH)(COD)] (M = Rh, Ir) to yield the corresponding early-late heterobimetallic complexes [TiCp*(thiosal)M(COD)] (M = Rh (2); Ir (3)). Carbon monoxide replaces the COD ligand in 2 and 3 leading to the respective dicarbonyl complexes [TiCp*(thiosal)M(CO)] (M = Rh (4); Ir (5)).

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si-O-CH[double bond, length as m-dash]CH and Si-(CH)C(CH) substituents via cleavage of tetrahydrofuran and trapping of its ring fragments.

The formation of a family of silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc(CH)C(CH)SiCH[double bond, length as m-dash]CH (5), Fc(CH[double bond, length as m-dash]CH-O)SiCH[double bond, length as m-dash]CH (6), Fc(OH)SiCH[double bond, length as m-dash]CH (7), Fc(CH[double bond, length as m-dash]CH-O)Si-O-Si(O-CH[double bond, length as m-dash]CH)Fc (8) and Fc(CH[double bond, length as m-dash]CH-O)Si-O-SiFc (9) is described. Silyl vinyl ether molecules 6, 8 and 9 and the heteroleptic vinylsilane 5 resulted from the competing metathesis reaction of lithioferrocene (FcLi), CH[double bond, length as m-dash]CH-OLi or (CH)C(CH)Li with the corresponding multifunctional chlorosilane, ClSiCH[double bond, length as m-dash]CH or ClSi-O-SiCl. The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent.

Binding Interactions between a Ferrocenylguanidinium Guest and Cucurbit[n]uril Hosts.

The binding interactions between a novel ferrocenylguanidinium derivative (FcG) and the macrocyclic hosts cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) were investigated in aqueous solution. H NMR spectroscopic experiments indicated that both hosts form stable 1:1 inclusion complexes with FcG, in which the ferrocenyl group is engulfed by the host cavity. The stoichiometry of the CB7·FcG complex was also confirmed by electrospray mass spectrometric (ESI MS) experiments.

New insights into the chemistry of di- and trimetallic iron dithiolene derivatives. Structural, Mössbauer, magnetic, electrochemical and theoretical studies.

Reaction of Fe3(CO)12 with 1,2-dithiolene HSC6H2Cl2SH affords a mixture of complexes [Fe2(CO)6(μ-SC6H2Cl2S)] 1, [Fe2(SC6H2Cl2S)4] 2 and [Fe3(CO)7(μ3-SC6H2Cl2S)2] 3. In the course of the reaction the trimetallic cluster 3 is first formed and then converted into the known dinuclear compound 1 to afford finally the neutral diiron tetrakis(dithiolato) derivative 2. Compounds 2 and 3 have been studied by Mössbauer spectroscopy, X-ray crystallography and theoretical calculations.

Mechanochemical and silica gel-mediated formation of highly electron-poor 1-cyanocarbonylferrocene.

Simple manual grinding of solid cyanomethylferrrocene (1) and silica gel provides a facile one-pot access route to prepare unexpected and highly electron-poor metallocene, 1-cyanocarbonylferrocene (2). Electrochemical measurements supported by computational studies reveal that 2 exhibits the highest Fe(II)/Fe(III) oxidation potential reported for mono-substituted ferrocenes.

Heterometallic platinum(II) compounds with β-aminoethylferrocenes: synthesis, electrochemical behaviour and anticancer activity.

A new family of heterometallic compounds 3-6 containing ferrocenyl and platinum(II) centers has been synthesized by reaction of 1-β-aminoethylferrocene (1) and 1,1'-bis(β-aminoethyl)ferrocene (2) with Pt(II) precursors. Using K(2)[PtCl(4)] as the Pt(II) source, the cis-square-planar neutral compounds [Fe{η(5)-C(5)H(4)(CH(2))(2)NH(2)}(2)PtCl(2)] (3) and [{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 of cis-[PtCl(2)(dmso)(2)] with 1 and 2 resulted in the displacement of dmso and chloride ligands from the platinum coordination sphere, affording the cationic and neutral compounds [Fe{η(5)-C(5)H(4)(CH(2))(2)NH(2)}(2)Pt(dmso)Cl]Cl (4) and [Fe(η(5)-C(5)H(4)(CH(2))(2)NH(2))(η(5)-C(5)H(5))Pt(dmso)Cl(2)] (6).

Pt(II)-activated coupling of aminoethylferrocene with benzonitrile. A facile access route to a new redox-active bis(ferrocenyl-amidine) anion sensor.

A new heterometallic electroactive compound having the ferrocenyl moiety attached to the platinum atom through an amidine functionality has been prepared via Pt(II)-mediated nucleophilic addition of β-aminoethylferrocene to a benzonitrile ligand. This neutral receptor shows remarkable electrochemical anion-sensing redox response to H(2)PO(4)(-).