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 via a convergent growth approach. Starting from triferrocenylvinylsilane Fc3SiCHCH2 (1) (Fc = Fe(η5-C5H4)(η5-C5H5) 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 (1H, 13C, 29Si) NMR spectroscopy, FT-IR and MALDI-TOF mass spectrometry, to establish their chemical structures and properties. The molecular structures of G1-dendron 3 and dendrimer 4, containing six and nine ferrocenyl units, respectively, have been successfully determined by single-crystal X-ray analysis, compound 4 being the branched multiferrocenyl-containing siloxane with the highest number of Fc substituents whose structure has been reported so far. Electrochemical studies (using cyclic voltammetry (CV) and square wave voltammetry (SWV) performed in dichloromethane solution with [PF6]- and [B(C6F5)]4- as supporting electrolyte anions of different coordinating abilities) reveal that all the macromolecular compounds obtained exhibit a three-wave redox pattern, suggesting appreciable electronic interactions between the silicon-bridged triferrocenyl moieties as they are successively oxidized. In addition, dendrimer 5 and dendronized polymers 7n-9n, with 12 and 4 < n < 14 ferrocenyl units, respectively, linked in threes around the periphery, undergo remarkable oxidative precipitation in CH2Cl2/[n-Bu4N][PF6] and are able to form chemically modified electrodes with stable electroactive films.

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(η5-C5H4)(η5-C5H5)) 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). The outcomes of these thiol-yne reactions showed a strong dependence on the initiation method used, with the thermally initiated one being the most efficient. These thiol-diferrocenylacetylene reactions mainly afforded the (Z)-stereoisomer of the newly obtained vinyl thioether sulfide FcCHC(Fc)S-(CH2)2OH (2), unlike the more common (E)-vinyl sulfides found in other additions to alkynes. The hydrothiolation of the internal -CC- bond in 1 was successfully extended to dithiol 2,2'-(ethylenedioxy)diethanethiol II, leading to the formation of the (ZZ)-isomer, with four ferrocenyl units, as the major product. According to the electrochemical studies, the new asymmetrical ferrocenyl-vinyl sulfides show iron-iron electronic and electrostatic interactions. Theoretical results for the (Z)-stereoisomer (2) suggest that adiabatic oxidation would lead to the loss of almost one electron on the ferrocenyl subunit closer to the thioether chain. Furthermore, the thiol-yne chemistry of the internal -CC- bond in diferrocenylacetylene has been compared to the external triple bond in ethynylferrocene, the theoretical results of which helped us to rationalize the very different reactivities observed in both metallocenes.

Facile Access to Hetero-poly-functional Arenes and meta-Substituted Arenes via Two-Step Dimetalation and Mg/Halogen-Exchange Protocol.

The Grignard reagent, iPrMgCl and its lithium chloride-enhanced 'turbo' derivative iPrMgCl⋅LiCl have been employed to investigate the single iodo/magnesium exchange reactions of the trisubstituted arenes, 2,5-diiodo-N,N-diisopropylbenzamide 1, 1,4-diiodo-2-methoxybenzene 2, and 1,4-diiodo-2-(trifluoromethyl)benzene 3. These three arenes themselves were initially prepared by a double ortho-, meta'-deprotonation of N,N-diisopropylbenzamide, anisole and (trifluoromethyl)benzene, respectively, using the sodium magnesiate reagent [Na4 Mg2 (TMP)6 (nBu)2 ] (where TMP is 2,2,6,6-tetramethylpiperidide), and subsequent electrophilic quenching with iodine/THF solution. Thus, by following a combined deprotonation and magnesium/halogen exchange strategy, the simple monosubstituted arenes can be converted to trisubstituted diiodoarenes, which can ultimately be transformed into the corresponding mono-magnesiated arenes, in THF at -40 °C, within seconds in good yields. The other functional group (OMe, NiPr2 or CF3 respectively) present on the di-iodoarenes helps direct the exchange reaction to the ortho position, whereas subsequent addition of different electrophiles permits the preparation of hetero-poly-functional-arenes, with three different substituents in their structure. Intriguingly, if water is used as the electrophile, a new and facile route to prepare meta-substituted arenes, which cannot be easily obtained by conventional processes, is forthcoming. In contrast to directed ortho-metalation (DoM) chemistry, this reaction sequence can be thought of as InDirect meta-Metalation (IDmM). The scope of the chemistry has been tested further by exposing the initial unreacted iodo-functionality at the meta-position to a second Mg/I-exchange reaction and subsequent functionalization.

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*Me3], Cp* = η5-C5Me5, with thiosalicylic acid (H2thiosal). Complex 1 reacts with [M(µ-OH)(COD)]2 (M = Rh, Ir) to yield the corresponding early-late heterobimetallic complexes [TiCp*(thiosal)2M(COD)] (M = Rh (2); Ir (3)). Carbon monoxide replaces the COD ligand in 2 and 3 leading to the respective dicarbonyl complexes [TiCp*(thiosal)2M(CO)2] (M = Rh (4); Ir (5)). Compound 4 reacts with PPh3 to yield the monocarbonyl derivative [TiCp*(thiosal)2Rh(CO)(PPh3)] (6). The reaction of compound 1 with LinBu yields the tetrametallic complex [{TiCp*(thiosal)2Li}2(THF)3(H2O)] (7). Compound 7 reacts with [RuCp*Cl(COD)] yielding the heterometallic complex [TiCp*(thiosal)2RuCp*] (8). The molecular structures of compounds 4, 5 and 7 have been studied by X-ray diffraction. From cyclic voltammetric (CV) and square wave voltammetric (SWV) experiments, we observed that attachment of the titanium moiety of precursor 1 to a late transition metal moiety through the sulfur atoms has a significant influence on the reduction behaviour of the Ti(iv) metal centre. Thus, monometallic 1 exhibits an irreversible reduction process at -1.15 V vs. SCE, whereas the CVs of heterobimetallic compounds 2-6 are characterized by the reversible or quasi-reversible one-electron reduction of the Ti(iv)/Ti(iii) system, suggesting a significant stabilization of the Ti(iii) reduced species. Likewise, substitution of the M(COD) diolefin fragment in 2 and 3 by the M(CO)2 carbonyl-containing moiety (in compounds 4 and 5) leads to a significant anodic shift in the titanium E1/2 reduction redox potentials.

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si-O-CH[double bond, length as m-dash]CH2 and Si-(CH2)2C(CH3)3 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 Fc2(CH3)3C(CH2)2SiCH[double bond, length as m-dash]CH2 (5), Fc2(CH2[double bond, length as m-dash]CH-O)SiCH[double bond, length as m-dash]CH2 (6), Fc2(OH)SiCH[double bond, length as m-dash]CH2 (7), Fc2(CH2[double bond, length as m-dash]CH-O)Si-O-Si(O-CH[double bond, length as m-dash]CH2)Fc2 (8) and Fc2(CH2[double bond, length as m-dash]CH-O)Si-O-SiFc3 (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), CH2[double bond, length as m-dash]CH-OLi or (CH3)3C(CH2)2Li with the corresponding multifunctional chlorosilane, Cl3SiCH[double bond, length as m-dash]CH2 or Cl3Si-O-SiCl3. The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent. Diferrocenylvinyloxyvinylsilane 6 is noteworthy since it represents a rare example of a redox-active silyl mononomer in which two different C[double bond, length as m-dash]C polymerisable groups are directly connected to silicon. The molecular structures of the silicon-containing multiferrocenyl species 5, 6, 8 and 9 have been investigated by single-crystal X-ray diffraction studies, demonstrating the capture and storage processes of two ring fragments resulting from the cleavage of cyclic THF in redox-active and stable crystalline organometallic compounds. From electrochemical studies we found that by changing the anion of the supporting electrolyte from [PF6]- to [B(C6F5)4]-, the redox behaviour of tetrametallic disiloxane 8 can be switched from a poorly resolved multistep redox process to four consecutive well-separated one-electron oxidations, corresponding to the sequential oxidation of the four ferrocenyl moieties.

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. 1H 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. The association equilibrium constants (K) were determined from NMR competition experiments. The measured K values were 3.5 × 109 and 2.5 × 108 M-1 for CB7 and CB8, respectively, in 50 mM sodium acetate-d3 D2O solution (pD 4.7). DFT computational studies confirmed the 1:1 stoichiometry and the inclusion character of both complexes. Voltammetric experiments were carried out to measure the complexation-induced shifts on the half-wave potentials for the one-electron oxidation of the ferrocenyl moiety. Complexation by CB7 led to a 12 mV anodic shift, while CB8 caused a larger 32 mV shift also in the positive direction. These potential shifts suggest that the delocalization of the positive charge on the side arm over the three nitrogens in the guanidinium unit results in electrochemical behavior similar to that observed with neutral ferrocene derivatives.

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. In compound 2 the metal atoms are in an intermediate-spin Fe(III) state (S(Fe) = 3/2) and each metal is bonded to a bridging dithiolene ligand and a non-bridging thienyl radical (S = 1/2). Magnetic measurements show a strong antiferromagnetic coupling in complex 2. Cyclic voltammetry experiments show that the mixed valence trinuclear cluster 3 undergoes a fully reversible one electron reduction. Additionally, compound 3 behaves as an electrocatalyst in the reduction process of protons to hydrogen.

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 ß-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-ß-aminoethylferrocene (1) and 1,1'-bis(ß-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). Compounds 3-6 were thoroughly characterized using multinuclear ((1)H, (13)C, (195)Pt) NMR, IR spectroscopy, ESI mass spectrometry and elemental analysis. Single-crystal X-ray analysis of heterometallic 6 confirmed the cis geometry of the molecule and revealed that the platinum atom is held in a perfect square-planar geometry. The electrochemical behaviour of the heterometallic compounds 3-6, which has been examined by cyclic (CV) and square wave (SWV) voltammetries in dichloromethane and dmso solution, is characterized by the reversible one-electron oxidation of the ferrocene moieties. The results of the biological activity studies revealed that the organometallic complex 5 is active against all cell lines with GI(50) values in the range 1.7-2.3 µM. When compared to the standard anticancer drug cisplatin, heterotrimetallic 5, possessing two aminoethylferrocenyl units coordinated to the Pt(II) center, showed a greater activity profile in the colon cancer cell line. Cell cycle studies revealed that the new mixed compound exhibits a mechanism of action different to cisplatin.

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 ß-aminoethylferrocene to a benzonitrile ligand. This neutral receptor shows remarkable electrochemical anion-sensing redox response to H(2)PO(4)(-).