Abdou K. Diallo

Ferrocenyl-terminated redox stars: synthesis and electrostatic effects in mixed-valence stabilization.

A family of rigid ferrocenyl-terminated redox stars has been synthesized--by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers--and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu(4)PF(6) as the supporting electrolyte on a Pt anode in CH(2)Cl(2), whereas three distinct two-electron reversible CV waves are observed using Nn-Bu(4)BAr(F)(4) (Ar(F) = 3,5-C(6)H(3)-(CF(3))(2)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu(4)PF(6) and three one-electron waves using Nn-Bu(4)BAr(F)(4). This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu(4)BAr(F)(4) as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu(4)BAr(F)(4), which is attributed to the transoïd conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, ΔE(p) is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoïd position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.

How Do Redox Groups Behave around a Rigid Molecular Platform? Hexa(ferrocenylethynyl)benzenes and Their Electrostatic Redox Chemistry

A new family of hexakis(ferrocenylethynyl)benzenes was synthesized by Negishi coupling from ethynylferrocenes and C(6)Br(6) and can be reversibly oxidized to stable hexaferrocenium salts (see picture, Ar(F)=[3,5-C(6)H(3)(CF(3))(2)]). Their cyclic voltammograms show a single six-electron wave, three distinct two-electron waves, or a cascade of six single-electron waves, depending on the electrolyte counterion and number of methyl substituents on the ferrocenyl groups.

Extremely Efficient Catalysis of Carbon-Carbon Bond Formation Using "Click" Dendrimer-Stabilized Palladium Nanoparticles

This article is an account of the work carried out in the authors’ laboratory illustrating the usefulness of dendrimer design for nanoparticle palladium catalysis. The “click” synthesis of dendrimers constructed generation by generation by 1→3 C connectivity, introduces 1,2,3-triazolyl ligands insides the dendrimers at each generation. Complexation of the ligands by PdII followed by reduction to Pd0 forms dendrimer-stabilized Pd nanoparticles (PdNPs) that are extremely reactive in the catalysis of olefin hydrogenation and C-C bond coupling reactions. The stabilization can be outer-dendritic for the small zeroth-generation dendrimer or intra-dendritic for the larger first- and second-generation dendrimers. The example of the Miyaura-Suzuki reaction that can be catalyzed by down to 1 ppm of PdNPs with a “homeopathic” mechanism (the less, the better) is illustrated here, including catalysis in aqueous solvents.

Olefin metathesis in nano-sized systems.

Summary The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i) The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP) or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM), cross metathesis (CM), enyne metathesis reactions (EYM) – for reactions in water without a co-solvent and (ii) construction and functionalization of dendrimers by CM reactions.

How do nitriles compare with isoelectronic alkynyl groups in the electronic communication between iron centers bridged by phenylenebis- and -tris(nitrile) ligands? An electronic and crystal-structure study.

Density functional theory (DFT) calculations on the model [{FeCp(dpe)}(2){1,4-C(6)H(4)(CN)(2)}](2+) (3(2+); dpe = diphosphinoethane) of salts of the cations [{FeCp(dppe)}(2){1,4-C(6)H(4)(CN)(2)}](2+) (1(2+); dppe = 1,2-bis[diphenyldiphosphino]ethane) and [{FeCp*(CO)(2)}(2){1,4-C(6)H(4)(CN)(2)}](2+) (2(2+)), for which the X-ray crystal structures have been determined, as well as on its isomer [{FeCp(dpe)}(2){1,3-C(6)H(4)(CN)(2)}](2+) (4(2+)) and on the related complex [{FeCp(dpe)}(3){1,3,5-C(6)H(3)(CN)(3)}](3+) (5(2+)), indicate that the highest occupied molecular orbitals (HOMOs) of these compounds are localized on the metal centers with negligible participation of the C(6) ring. Thus, the poly(nitrile)phenylene ligand efficiently quenches the electronic communication between the metal centers. This is at variance with the related isoelectronic polyacetylene phenylene complexes, in which the iron centers have been shown to be electronically coupled. Consistently, apart from the case of 3(3+), which shows some degree of delocalization, all of the oxidized forms of 3(2+), 4(2+), and 5(2+) can be described as class II, localized mixed-valent species, in agreement with the electrochemical data showing two close oxidation potentials around 1 V vs FeCp*(2). This is at variance with the p-phenylene-bridged biethynyldiiron analogue, for which extended electronic delocalization was earlier shown to provide greater degree of delocalization of the mixed valency. Time-dependent DFT calculations on 3(2+), 4(2+), and 5(2+) indicate that the lowest-energy absorption band is associated with metal-to-ligand charge-transfer transitions involving the metallic HOMOs and the two lowest unoccupied molecular orbitals that derive from the lowest π*(phenylene) orbitals with some π*(CN) bonding admixture.

Visible-light generation of the naked 12-electron fragment C5H5Fe+: alkyne-to-vinylidene isomerization and synthesis of polynuclear iron vinylidene and alkynyl complexes including hexairon stars.

Visible-light photolysis of [FeCp(η(6)-C(6)H(5)CH(3))][PF(6)] using a simple 100-W bulb or a compact fluorescent light bulb in the presence of terminal alkynes and dppe yielded the vinylidene complexes [FeCp(═C═CHR)(dppe)][PF(6)] that were deprotonated by t-BuOK to yield the alkynyl complexes [FeCp(-C≡CR)(dppe)]. The reaction has been extended to the synthesis of bis-, tris, tetra-, and hexanuclear iron complexes including three alkynes of the ferrocenyl family.

Review: Mixed-valent metallodendrimers: design and functions

Various types of mixed-valent metallodendrimers and star-shaped macromolecules containing ferrocenyl, biferrocenyl, or other redox-robust iron groups with rigid or flexible tethers of short and long lengths mostly studied in the authors’ laboratory including the class type in terms of Robin-Day classification and their functions including electrode modification, sensing, and nanoparticle templates are discussed in this mini review. Graphical Abstract

Dendritic Molecular Nanobatteries and the Contribution of Click Chemistry

This article is a mini-review mostly based on the work of the authors’ laboratory on the redox chemistry of metallodendrimers and gold nanoparticles, with emphasis on “click” chemistry. Late transition-metal sandwich complexes possess a rather unique ability to withstand two or three oxidation states without breakdown, especially with permethylated π-cyclopentadienyl or arene ligands. When they are linked to dendritic cores, the assembled nano-systems undergo chemically and electrochemically reversible transfer of a large number of electrons (up to 14,000). These multiple redox processes are useful for nanodevices behaving as nanobatteries for redox sensing, modified electrode surfaces and redox catalysis. Click chemistry was recently disclosed as one of the most powerful means to form such assemblies including both arene-cored and gold nanoparticle-cored dendrimers.