RESUMO
Several strategies are available to design well-defined multimetallic molecular entities bearing functional ligands. Substoichiometric exchange reactions in the coordination sphere of pre-existing multinuclear precursors are relatively underexploited in this context. Palladium(II) acetate is not a mononuclear compound in the solid state but rather exists as a trimer, i. e. [Pd3(OAc)6]. Although this material is ubiquitously used to synthesize mononuclear Pd species, it may principally also lend itself to selective exchange of some of the edge-sharing acetate units in its triangular motif, whilst keeping the overall multinuclear architecture intact. Strikingly, little is known about the controlled manipulation and substoichiometric substitution chemistry of this well-defined conglomerate. We herein conclusively demonstrate that, for the first time, the targeted exchange of two or four acetate units from the Pd3(acetate)6 platform is possible, thereby installing either one or two new tridentate ligands onto this trinuclear architecture. Follow-up exchange and substitution chemistry is available without disrupting the multimetallic nature of the core structure. New complexes 2-7 are all conclusively characterized using multinuclear NMR spectroscopy, UV-vis and IR spectroscopy as well as X-ray diffraction analysis.
RESUMO
Here, we present the development and characterization of the novel PhenTAA macrocycle as well as a series of [Ni(R2PhenTAA)]n complexes featuring two sites for ligand-centered redox-activity. These differ in the substituent R (R = H, Me, or Ph) and overall charge of the complex n (n = -2, -1, 0, +1, or +2). Electrochemical and spectroscopic techniques (CV, UV/vis-SEC, X-band EPR) reveal that all redox events of the [Ni(R2PhenTAA)] complexes are ligand-based, with accessible ligand charges of -2, -1, 0, +1, and +2. The o-phenylenediamide (OPD) group functions as the electron donor, while the imine moieties act as electron acceptors. The flanking o-aminobenzaldimine groups delocalize spin density in both the oxidized and reduced ligand states. The reduced complexes have different stabilities depending on the substituent R. For R = H, dimerization occurs upon reduction, whereas for R = Me/Ph, the reduced imine groups are stabilized. This also gives electrochemical access to a [Ni(R2PhenTAA)]2- species. DFT and TD-DFT calculations corroborate these findings and further illustrate the unique donor-acceptor properties of the respective OPD and imine moieties. The novel [Ni(R2PhenTAA)] complexes exhibit up to five different ligand-based oxidation states and are electrochemically stable in a range from -2.4 to +1.8 V for the Me/Ph complexes (vs Fc/Fc+).
RESUMO
Nonclassical P(III) centers have attracted much attention in recent years. Incorporating a P(III) center in a rigid bicyclic platform offers a particularly attractive way to invoke significant geometric distortion of the phosphorus atom that may in turn induce unusual reactivity. Although still relatively scarcely explored, phosphorus centers enforced in a non-C3 symmetry have gained significant traction lately. However, the current scaffolds are based on a relatively limited set of design principles and ligand platforms associated therewith. This work is focussed on the synthesis as well as versatile oxidation, addition and coordination chemistry of a geometrically distorted P(III) species featuring a synthetically modular, nonsymmetric trisamine platform derived from 2-(methylamino)-N-(2-(methylamino)phenyl)benzenesulfonamide.
RESUMO
Photoredox catalysis is a valuable tool in a large variety of chemical reactions. Main challenges still to be overcome are photodegradation of photocatalysts and substrates, short lifetimes of reactive intermediates, and selectivity issues due to unwanted side reactions. A potential solution to these challenges is the pre-organization of the photosensitizer, substrate and (co)-catalyst in supramolecular self-assembled structures. In such architectures, (organic) dyes can be stabilized, and higher selectivity could potentially be achieved through pre-organizing desired reaction partners via non-covalent interactions. Perylene diimide (PDI) is an organic dye, which can be readily reduced to its mono- and dianion. Excitation of both anions leads to highly reducing excited states, which are able to reduce a variety of substrates via single electron transfer. The incorporation of PDI into a heteroleptic [M4La2Lb2] supramolecular square has been recently demonstrated. Herein we investigate its photophysical properties and demonstrate that incorporated PDI indeed features photocatalytic activity. Initial results suggest that the pre-organisation by binding positively affects the outcome.
RESUMO
In this paper, we report the synthesis of a unique silicon(I)-based metalla-disilirane and report on its reactivity toward TMS-azide and benzophenone. Metal complexes containing disilylenes ((bis)silylenes with a Si-Si bond) are known, but direct ligation of the Si(I) centers to transition metals always generated dinuclear species. To overcome this problem, we targeted the formation of a mononuclear iron(0)-silicon(I)-based disilylene complex via templated synthesis, starting with ligation of two Si(II) centers to iron(II), followed by a two-step reduction. The DFT structure of the resulting η2-disilylene-iron complex reveals metal-to-silicon π-back donation and a delocalized three-center-two-electron (3c-2e) aromatic system. The Si(I)-Si(I) bond displays unusual but well-defined reactivity. With TMS-azide, both the initial azide adduct and the follow-up four-membered nitrene complex could be isolated. Reaction with benzophenone led to selective 1,4-addition into the Si-Si bond. This work reveals that selective reactions of Si(I)-Si(I) bonds are made possible by metal ligation.
RESUMO
The cobalt species PPh4 [CoIII (TAMLred )] is a competent and stable catalyst for the sulfimidation of (aryl)(alkyl)-substituted sulfides with iminoiodinanes, reaching turnover numbers up to 900 and turnover frequencies of 640â min-1 under mild and aerobic conditions. The sulfimidation proceeds in a highly chemoselective manner, even in the presence of alkenes or weak C-H bonds, as supported by inter- and intramolecular competition experiments. Functionalization of the sulfide substituent with various electron-donating and electron-withdrawing arenes and several alkyl, benzyl and vinyl fragments is tolerated, with up to quantitative product yields. Sulfimidation of phenyl allyl sulfide led to [2,3]-sigmatropic rearrangement of the initially formed sulfimide species to afford the corresponding N-allyl-S-phenyl-thiohydroxylamines as attractive products. Mechanistic studies suggest that the actual nitrene transfer to the sulfide proceeds via (previously characterized) electrophilic nitrene radical intermediates that afford the sulfimide products via electronically asynchronous transition states, in which SET from the sulfide to the nitrene radical complex precedes N-S bond formation in a single concerted process.
RESUMO
Catalysis in confined spaces, such as those provided by supramolecular cages, is quickly gaining momentum. It allows for second coordination sphere strategies to control the selectivity and activity of transition metal catalysts, beyond the classical methods like fine-tuning the steric and electronic properties of the coordinating ligands. Only a few electrocatalytic reactions within cages have been reported, and there is no information regarding the electron transfer kinetics and thermodynamics of redox-active species encapsulated into supramolecular assemblies. This contribution revolves around the preparation of M6L12 and larger M12L24 (M = Pd or Pt) nanospheres functionalized with different numbers of redox-active probes encapsulated within their cavity, either in a covalent fashion via different types of linkers (flexible, rigid and conjugated or rigid and nonconjugated) or by supramolecular hydrogen bonding interactions. The redox probes can be addressed by electrochemical electron transfer across the rim of nanospheres, and the thermodynamics and kinetics of this process are described. Our study identifies that the linker type and the number of redox probes within the cage are useful handles to fine-tune the electron transfer rates, paving the way for the encapsulation of electroactive catalysts and electrocatalytic applications of such supramolecular assemblies.
RESUMO
The redox noninnocence of the TAML scaffold in cobalt-TAML (tetra-amido macrocyclic ligand) complexes has been under debate since 2006. In this work, we demonstrate with a variety of spectroscopic measurements that the TAML backbone in the anionic complex [CoIII(TAMLred)]- is truly redox noninnocent and that one-electron oxidation affords [CoIII(TAMLsq)]. Multireference (CASSCF) calculations show that the electronic structure of [CoIII(TAMLsq)] is best described as an intermediate spin (S = 1) cobalt(III) center that is antiferromagnetically coupled to a ligand-centered radical, affording an overall doublet (S = 1/2) ground-state. Reaction of the cobalt(III)-TAML complexes with PhINNs as a nitrene precursor leads to TAML-centered oxidation and produces nitrene radical complexes without oxidation of the metal ion. The ligand redox state (TAMLred or TAMLsq) determines whether mono- or bis-nitrene radical complexes are formed. Reaction of [CoIII(TAMLsq)] or [CoIII(TAMLred)]- with PhINNs results in the formation of [CoIII(TAMLq)(Nâ¢Ns)] and [CoIII(TAMLq)(Nâ¢Ns)2]-, respectively. Herein, ligand-to-substrate single-electron transfer results in one-electron-reduced Fischer-type nitrene radicals (Nâ¢Ns-) that are intermediates in catalytic nitrene transfer to styrene. These nitrene radical species were characterized by EPR, XANES, and UV-vis spectroscopy, high-resolution mass spectrometry, magnetic moment measurements, and supporting CASSCF calculations.
RESUMO
Three Pt4 L2 L'2 heteroleptic rectangles (1-3), containing ditopic redox-active bis-pyridine functionalized perylene bisimide (PBI) ligands PBI-pyr2 (L) are reported. Co-ligand L' is a dicarboxylate spacer of varying length, leading to modified overall size of the assemblies. 1 Hâ NMR spectroscopy reveals a trend in the splitting and upfield chemical shift of the PBI-hydrogens in the rectangles with respect to free PBI, most pronounced with the largest strut length (3) and least with the smallest strut length (1). This is attributed to increased rotational freedom of the PBI-pyr2 ligand over its longitudinal axis (Npy -Npy ), due to increased distance between the PBI-surfaces, which is corroborated by VT-NMR measurements and DFT calculations. The intramolecular motion entails desymmetrization of the two PBI-ligands, in line with cyclic voltammetry (CV) data. The first (overall two-electron) reduction event and re-oxidation for 1 display a subtle peak-to-peak splitting of 60â mV, whilst increased splitting of this event is observed for 2 and 3. The binding of pyrene in 1 is probed to establish proof of concept of host-guest chemistry enabled by the two PBI-motifs. Fitting the binding curve obtained by 1 Hâ NMR titration with a 1:1 complex formation model led to a binding constant of 964±55 m-1 . Pyrene binding is shown to directly influence the redox-chemistry of 1, resulting in a cathodic and anodic shift of approximately 46â mV on the first and second reduction event, respectively.
RESUMO
1,1,2,2-Tetracyanocyclopropane derivatives 1 and 2 were designed and synthesized to probe the utility of sp3 -C centred tetrel bonding interactions in crystal engineering. The crystal packing of 1 and 2 and their 1,4-dioxane cocrystals is dominated by sp3 -C(CN)2 â â â O interactions, has significant Câ â â O van der Waals overlap (≤0.266â Å) and DFT calculations indicate interaction energies of up to -11.0â kcal mol-1 . A cocrystal of 2 with 1,4-thioxane reveals that the cyclopropane synthon prefers interacting with O over S. Computational analyses revealed that the electropositive C2 (CN)4 pocket in 1 and 2 can be seen as a strongly directional 'tetrel-bond donor', similar to halogen bond or hydrogen bond donors. This disclosure is expected to have implications for the utility of such 'tetrel bond donors' in molecular disciplines such as crystal engineering, supramolecular chemistry, molecular recognition and medicinal chemistry.
RESUMO
Incorporation of 2,5-dihydroxyterephthalate as a covalent scaffold in the axis of a 30-membered all-carbon macrocycle provides access to a modular series of rotaxanes. Installment of tethered alkynes or azides onto the terephthalic phenolic hydroxyl functionalities, which are situated at opposite sides of the macrocycle, gives versatile prerotaxane building blocks. The corresponding [2]rotaxanes are obtained by introduction of bulky stoppering ("capping") units at the tethers and subsequent cleavage of the covalent ring/thread ester linkages. Extension of this strategy via coupling of two prerotaxanes bearing complementary linker functionalities (i.e., azide and alkyne) and follow-up attachment of stopper groups provide efficient access to [n]rotaxanes. The applicability and modular nature of this novel approach were demonstrated by the synthesis of a series of [2]-, [3]-, and [4]rotaxanes. Furthermore, it is shown that the prerotaxanes allow late-stage functionalization of the ring fragment introducing further structural diversity.
RESUMO
The influence of a redox-active ligand on spin-changing events induced by the coordination of exogenous donors is investigated within the cobalt complex [CoII(DPP·2-)], bearing a redox-active DPP2- ligand (DPP = dipyrrin-bis(o,p-di-tert-butylphenolato) with a pentafluorophenyl moiety on the meso-position. This square-planar complex was subjected to the coordination of tetrahydrofuran (THF), pyridine, tBuNH2, and AdNH2 (Ad = 1-adamantyl), and the resulting complexes were analyzed with a variety of experimental (X-ray diffraction, NMR, UV-visible, high-resolution mass spectrometry, superconducting quantum interference device, Evans' method) and computational (density functional theory, NEVPT2-CASSCF) techniques to elucidate the respective structures, spin states, and orbital compositions of the corresponding octahedral bis-donor adducts, relative to [CoII(DPP·2-)]. This starting species is best described as an open-shell singlet complex containing a DPP·2- ligand radical that is antiferromagnetically coupled to a low-spin (S = 1/2) cobalt(II) center. The redox-active DPPn- ligand plays a crucial role in stabilizing this complex and in its facile conversion to the triplet THF adduct [CoII(DPP·2-)(THF)2] and closed-shell singlet pyridine and amine adducts [CoIII(DPP3-)(L)2] (L = py, tBuNH2, or AdNH2). Coordination of the weak donor THF to [CoII(DPP·2-)] changes the orbital overlap between the DPP·2- ligand radical π-orbitals and the cobalt(II) metalloradical d-orbitals, which results in a spin-flip to the triplet ground state without changing the oxidation states of the metal or DPP·2- ligand. In contrast, coordination of the stronger donors pyridine, tBuNH2, or AdNH2 induces metal-to-ligand single-electron transfer, resulting in the formation of low-spin (S = 0) cobalt(III) complexes [CoIII(DPP3-)(L)2] containing a fully reduced DPP3- ligand, thus explaining their closed-shell singlet electronic ground states.
RESUMO
The metalloradical activation of o-aryl aldehydes with tosylhydrazide and a cobalt(II) porphyrin catalyst produces cobalt(III)-carbene radical intermediates, providing a new and powerful strategy for the synthesis of medium-sized ring structures. Herein we make use of the intrinsic radical-type reactivity of cobalt(III)-carbene radical intermediates in the [CoII (TPP)]-catalyzed (TPP=tetraphenylporphyrin) synthesis of two types of 8-membered ring compounds; novel dibenzocyclooctenes and unprecedented monobenzocyclooctadienes. The method was successfully applied to afford a variety of 8-membered ring compounds in good yields and with excellent substituent tolerance. Density functional theory (DFT) calculations and experimental results suggest that the reactions proceed via hydrogen atom transfer from the bis-allylic/benzallylic C-H bond to the carbene radical, followed by two divergent processes for ring-closure to the two different types of 8-membered ring products. While the dibenzocyclooctenes are most likely formed by dissociation of o-quinodimethanes (o-QDMs) which undergo a non-catalyzed 8π-cyclization, DFT calculations suggest that ring-closure to the monobenzocyclooctadienes involves a radical-rebound step in the coordination sphere of cobalt. The latter mechanism implies that unprecedented enantioselective ring-closure reactions to chiral monobenzocyclooctadienes should be possible, as was confirmed for reactions mediated by a chiral cobalt-porphyrin catalyst.
RESUMO
Direct synthetic routes to amidines are desired, as they are widely present in many biologically active compounds and organometallic complexes. N-Acyl amidines in particular can be used as a starting material for the synthesis of heterocycles and have several other applications. Here, we describe a fast and practical copper-catalyzed three-component reaction of aryl acetylenes, amines, and easily accessible 1,4,2-dioxazol-5-ones to N-acyl amidines, generating CO2 as the only byproduct. Transformation of the dioxazolones on the Cu catalyst generates acyl nitrenes that rapidly insert into the copper acetylide Cu-C bond rather than undergoing an undesired Curtius rearrangement. For nonaromatic dioxazolones, [Cu(OAc)(Xantphos)] is a superior catalyst for this transformation, leading to full substrate conversion within 10 min. For the direct synthesis of N-benzoyl amidine derivatives from aromatic dioxazolones, [Cu(OAc)(Xantphos)] proved to be inactive, but moderate to good yields were obtained when using simple copper(I) iodide (CuI) as the catalyst. Mechanistic studies revealed the aerobic instability of one of the intermediates at low catalyst loadings, but the reaction could still be performed in air for most substrates when using catalyst loadings of 5 mol %. The herein reported procedure not only provides a new, practical, and direct route to N-acyl amidines but also represents a new type of C-N bond formation.
RESUMO
Controlled ligand-based redox-activity and chemical non-innocence are rapidly gaining importance for selective (catalytic) processes. This Concept aims to provide an overview of the progress regarding ligand-to-substrate single-electron transfer as a relatively new mode of operation to exploit ligand-centered reactivity and catalysis based thereon.
RESUMO
Ligands with reactive carbon sites in the periphery of a metal center have emerged as a powerful approach for metal-ligand bond activation. These reactive carbon sites are commonly generated by deprotonation strategies. Carbon-silicon bond cleavage is a potential alternative to access such constructs. Herein, the monodesilylation of bis-silyl-substituted P,N scaffold PNSi2 in the coordination sphere of [RhI (Cl)(CO)(PNSi2 )] (1) with sodium azide is disclosed. This affords a unique dinucleating anionic κ2 -C,N-κ1 -P ligand with a carbanionic methine carbon atom directly bound to rhodium as part of a four-membered Rh-N-C-C rhodacycle. This dimer undergoes meta-pyridine C-H activation facilitated by weak bases, which leads to a desymmetrization of the system and provides a σ,π-bridging 3-pyridyl fragment bound to RhI . The facile Si-C cleavage strategy may pave the way to studying the reactivity and functionalization of a variety of κ2 -C,N-coordinated pyridine scaffolds for selective transformations.
RESUMO
A new method for the one-step C-H amination of xanthene and thioxanthene with sulfonamides is reported, without the need for any metal catalyst. A benzoquinone was employed as a hydride (or two-electron and one-proton) acceptor. Moreover, a previously unknown and uncatalyzed reaction between iminoiodanes and xanthene, thioxanthene and dihydroacridines (9,10-dihydro-9-heteroanthracenes or dihydroheteroanthracenes) is disclosed. The reactions proceed through hydride transfer from the heteroarene substrate to the iminoiodane or benzoquinone, followed by conjugate addition of the sulfonamide to the oxidized heteroaromatic compounds. These findings may have important mechanistic implications for metal-catalyzed C-H amination processes involving nitrene transfer from iminoiodanes to dihydroheteroanthracenes. Due to the weak C-H bond, xanthene is an often-employed substrate in mechanistic studies of C-H amination reactions, which are generally proposed to proceed via metal-catalyzed nitrene insertion, especially for reactions involving nitrene or imido complexes that are less reactive (i.e., less strongly oxidizing). However, these substrates clearly undergo non-catalyzed (proton-coupled) redox coupling with amines, thus providing alternative pathways to the widely assumed metal-catalyzed pathways.
RESUMO
Two novel κ2-C,N-pyridine bridged [FeFe]-H2ase mimics (1 and 2) have been prepared and are shown to function as efficient molecular catalysts for electrocatalytic proton reduction. The elemental and structural composition of the complexes are confirmed by NMR and IR spectroscopy, high-resolution mass spectrometry and single-crystal X-ray diffraction. Electrochemical investigations reveal that the complexes reduce protons at their first reduction potential, resulting in the lowest overpotential (120 mV) ever reported for [FeFe]-H2ase mimics in proton reduction catalysis when mild acid (phenol) is used as proton source.
RESUMO
Based on previous work related to the design and application of rigid tridentate phosphine-pyridine-phenyl coordination offered by a PNC-pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox-reactivity of two NiII(PNC) complexes featuring either a methyl (2CH3 ) or CF3 co-ligand (2CF3 ) are described. One-electron oxidation is proposed to furnish C-C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study. One-electron reduction results in a ligand-centered radical anion, as supported by electrochemistry, UV spectroelectrochemistry, EPR spectroscopy, and DFT calculations. This further attenuates the breadth of chemical reactivity offered by such PNC-pincer ligands.
RESUMO
The metalloradical activation of ortho-benzallylaryl N-tosyl hydrazones with [Co(TPP)] (TPP=tetraphenylporphyrin) as the catalyst enabled the controlled exploitation of the single-electron reactivity of the redox non-innocent carbene intermediate. This method offers a novel route to prepare eight-membered rings, using base metal catalysis to construct a series of unique dibenzocyclooctenes through selective Ccarbene -Caryl cyclization. The desired eight-membered-ring products were obtained in good to excellent yields. A large variety of aromatic substituents are tolerated. The proposed reaction mechanism involves intramolecular hydrogen atom transfer (HAT) to CoIII -carbene radical intermediates followed by dissociation of an ortho-quinodimethane that undergoes 8πâ cyclization. The mechanism is supported by DFT calculations, and the presence of radical-type intermediates was confirmed by trapping experiments.