RESUMEN

Geometrically-constrained pnictogen pincer complexes have emerged in recent years as platforms for unique stoichiometric and catalytic chemical transformations. These complexes feature dynamic conformations ranging from fully planar at the pnictogen centre to distorted-pyramidal geometries, as well as variation between phases. Although the valued reactivity of pnictogen pincer complexes is ascribed to their geometries, there is no unified model to explain the observed conformational outcomes across different ligands and pnictogen centres. Here we propose such a model through computational analysis of more than 1300 structures across 64 complexes (16 ligands and 4 heavy pnictogens), explaining the experimental observations and making new predictions. By looking at signatures of bond stability (bond lengths, Wiberg bond indices) and delocalization (NPA charges, Hirshfeld charges), our framework posits a pnictogen-based σ-bonding effect that favours pyramidalization and exists in competition with a ligand-based π-bonding effect that favours planarity. Variations in structure as a function of pnictogen identity, ligand tethering, electronics, and aromaticity can be reconciled with reference to a balance between these two opposing forces. Careful consideration of the σ/π-bonding effects may aid in the rational design of future pnictogen pincer complexes with predictable geometries and reactivities.

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This work describes the synthesis of eight new Pd(II) and Pt(II) complexes with the general formula [M(TSC)Cl], where TSC represents the 4N-monosubstituted thiosemicarbazone derived from 2-acetylpyridine N-oxide with the substituents CH3 (H4MLO), C2H5 (H4ELO), phenyl (H4PLO) and (CH3)2 (H4DMLO). These complexes have been characterized by elemental analysis, molar conductivity, IR spectroscopy, 1H, 13C, 195Pt and ESI-MS. The complexes exhibit a square planar geometry around the metallic center coordinated by a thiosemicarbazone molecule acting as a donor ONS-type pincer ligand and by a chloride, as confirmed by the molecular structures of the complexes, [Pd(4ELO)Cl] (3) and [Pd(4PLO)Cl] (5), determined by single-crystal X-ray diffraction. The 195Pt NMR spectra of the complexes of formulae [Pt(4PLO)Cl] (6) and [Pt(4DMLO)Cl] (8) in DMSO show a single signal at -2420.4 ppm, confirming the absence of solvolysis products. Complexes 3 and 5 have been tested as catalysts in the Suzuki-Miyaura cross-coupling reactions of aryl bromides with phenylboronic acid, with yields of between 50 and 90.

RESUMEN

To evaluate bifunctional ligand reactivity involving NH acidic sites in the secondary coordination sphere of metal complexes, complexes where the proton has been substituted with a methyl group (NMe) are often investigated. An alternative strategy would involve substitution of the NH group for an O. This contribution considers and compares the merits of these approaches; the synthesis and characterization of cationic square planar Rh carbonyl complexes bearing diprotic bispyrazole pyridine ligand L1, and the bis-methylated pyrazole pyridine ligand L1Me are described. The syntheses and characterization of the novel monoprotic pyrazole isoxazole pyridine ligand L2 and aprotic bisisoxazole pyridine ligand L3, and their corresponding Rh carbonyl complexes are also described. The different CO stretching frequencies of all four Rh-complexes suggest that substitutions of NH with NMe, as well as O, lead to significant electronic differences, and these differences are further demonstrated to lead to different ligand addition/substitution reactivities of the four isoelectronic Rh-complexes. Overall, the results suggest that the electronic differences arising due to NH substitutions can be significant and must be accounted for prior to invoking the participation of the proton.

RESUMEN

We report the rhodium(I) complex [Rh(CNC-NDI)(CO)]+ , in which CNC-NDI refers to a pincer-CNC ligand decorated with a naphthalenediimide moiety. Due to the presence of the planar CNC ligand and the naphthalenediimide moiety, the electronic nature of the complex can be modulated by means of supramolecular and redox stimuli, respectively. The metal complex shows a strong π-π-stacking interaction with coronene. This interaction has an impact on the electron-richness of the metal, as demonstrated by the shifting of the ν(CO) stretching band to a lower frequency. The addition of tetrabutylammonium fluoride facilitates the sequential one- and two-electron reduction of the NDI moiety of the ligand, thus resulting in a situation in which the ligand can increase its electron-donor strength in two levels. The nature of the interaction with the fluoride anion was studied computationally. The catalytic activity of the [Rh(CNC-NDI)(CO)]+ complex was tested in the cycloisomerization of alkynoic acids, where it is observed that the activity of the catalyst can be modulated between four levels of activity, which correspond to i) the use of the unmodified catalyst, ii) catalyst+coronene, iii) catalyst+2 equivalents of fluoride, and iv) catalyst+5 equivalents of fluoride.

RESUMEN

Alzheimer's disease (AD) is the most common form of dementia worldwide, affecting millions of people around the globe. AD is characterized by different pathologies being beta-amyloid (Aß) plaque formation, metal ion dysregulation, and oxidative stress (OS) central topics under investigation. Copper-Aß complexes have been shown to induce catalytic hydrogen peroxide formation and increase OS in the brain leading to neuronal death. Pincer-type compounds are tridentate ligands that coordinate metals in a planar fashion whose properties can be tuned via group substitutions, giving rise to many possibilities in catalysis and drug discovery. In this work we evaluated the potential pharmaceutical activity of 26 pincer compounds in AD's copper ion-related oxidative stress framework. In this sense, four key aspects were considered: 1) Lipinski's rule of five, 2) blood-brain barrier permeation, 3) standard reduction potential (SRP) of the formed copper complexes, and 4) the ligand's affinity towards copper cations. The evaluation of these criteria was performed by means of bioinformatic tools and electronic structure calculations at the DFT level of theory. Our results suggest that two compounds from this set are potential antioxidant agents, whereas five of them are promissory distributor-like compounds in the context of AD.

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RESUMEN

1 H NMR studies using a cationic complex with a pyridine-di-imidazolylidene pincer ligand of formula [Rh(CNC)(CO)]+ revealed that this compound showed high binding affinity with coronene in CH2 Cl2 . The interaction between coronene and the planar RhI complex is established by means of π-stacking interactions. This interaction has a strong impact on the electron-donating strength of the pincer CNC ligand, which is increased significantly, as demonstrated by the shifting of the ν(CO) stretching bands to lower frequencies. The addition of coronene increases the reaction rate of the nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, and also has a positive effect on the performance of the complex as a catalyst in the cycloisomerization of 4-pentynoic acid. These findings highlight the importance of supramolecular interactions for tuning the reactivity and catalytic activity of square-planar metal complexes.

RESUMEN

The steric tuning of a tridentate acridane-derived NNN pincer ligand allows for the isolation of a strictly T-shaped phosphine that exhibits ambiphilic reactivity. Well-defined phosphorus-centered reactivity towards nucleophiles and electrophiles is reported, contrasting with prior reports on this class of compounds. Reactions towards oxidants are also described. The latter result in the two-electron oxidation of the phosphorus atom from +III to +V and are accompanied by a strong geometric distortion of the NNN pincer ligand. By contrast, cooperative activation of E-H (HCl, HBcat, HOMe) bonds proceeds with retention of the phosphorus redox state. When using H2 O as a substrate, the reaction results in the full disassembly of H2 O to its constituent atoms, highlighting the potential of this platform for small molecule activation reactions.

RESUMEN

Nine ruthenium CNC pincer complexes (1-9) were tested for anticancer activity in cell culture under both dark and light conditions. These complexes included varied CNC pincer ligands including OH, OMe, or Me substituents on the pyridyl ring and wingtip N-heterocyclic carbene (NHC) groups which varied as methyl (Me), phenyl (Ph), mesityl (Mes), and 2,6-diisopropylphenyl (Dipp). The supporting ligands included acetonitrile, Cl, and 2,2'-bipyridine (bpy) donors. The synthesis of complexes 8 and 9 is described herein and are fully characterized by spectroscopic (1H NMR, IR, UV-Vis, MS) and analytical techniques. Single crystal X-ray diffraction results are reported herein for 8 and 9. The other complexes (1-7) are reported elsewhere. The four most lipophilic ruthenium complexes (6, 7, 8, and 9) showed the best activity vs. MCF7 cancer cells with complexes 6 and 9 showing cytotoxicity and complex 7 and 8 showing light activated photocytotoxicity. The distribution of these compounds between octanol and water is reported as log(Do/w) values, and increasing log(Do/w) values correlate roughly with improved activity vs. cancer cells. Overall, lipophilic wingtip groups (e.g. Ph, Mes, Dipp) on the NHC ring and a lower cationic charge (1+ vs. 2+) appears to be beneficial for improved anticancer activity.

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We report the synthesis of molybdenum and tungsten bromo dicarbonyl complexes (POCOPtBu)MIIBr(CO)2 (M = Mo or W; POCOPtBu = κ3-C6H3-1,3-[OP(tBu)2]2) supported by an anionic PCP pincer ligand, and the chromium complex (PNPtBu)Cr0(CO)3 (PNPtBu = 2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) bearing a neutral PNP pincer scaffold. The three group six complexes described in this study have been characterized by Liquid Injection Field Desorption Ionization Mass Spectrometry (LIFDI-MS), NMR, and IR spectroscopy. Single crystal X-ray diffraction studies show the MoII and WII complexes adopt a six-coordinate distorted trigonal prismatic geometry, whereas the Cr0 complex exhibits a distorted octahedral geometry.

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DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection of ketones have been carried out at the PBE0-D3PCM //RI-BP86PCM level. Mn complexes of an enantiomerically pure chiral P,N,N ligand have been found to be most reactive when adopting a facial coordination mode. The use of a new ligand with an ortho-substituted dimethylamino-pyridine motif has been calculated to completely transform the levels of enantioselectivity possible for the hydrogenation of cyclic ketones relative to the first-generation Mn catalysts. In silico evaluation of substrates has been used to identify those likely to be reduced with high enantiomer ratios (er), and others that would exhibit less selectivity; good agreements were then found in experiments. Various cyclic ketones and some acetophenone derivatives were hydrogenated with er's up to 99 : 1.

RESUMEN

The reaction of TaMe3 Cl2 with the rigid acridane-derived trisamine H3 NNN yields the tantalum(V) complex [TaCl2 (NNNcat )]. Subsequent reaction with dioxygen results in the full four-electron reduction of O2 yielding the oxido-bridged bimetallic complex [{TaCl2 (NNNsq )}2 O]. This dinuclear complex features an open-shell ground state due to partial ligand oxidation and was comprehensively characterized by single crystal X-ray diffraction, LIFDI mass spectrometry, NMR, EPR, IR and UV/VIS/NIR spectroscopy. The mechanism of O2 activation was investigated by DFT calculations revealing initial binding of O2 to the tantalum(V) center followed by complete O2 scission to produce a terminal oxido-complex.

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RESUMEN

Manganese-catalyzed hydrogenation reactions have aroused widespread interest in recent years. Among the catalytic systems described, especially PNP- and NNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, ketones, nitriles, aldimines and esters. Furthermore, NNP-Mn pincer compounds are efficient catalysts for the hydrogenolysis of less reactive amides, ureas, carbonates, and carbamates. Herein, the synthesis and application of specific imidazolylaminophosphine ligands and the corresponding Mn pincer complexes are described. These new catalysts have been characterized and studied by a combination of experimental and theoretical investigations, and their catalytic activities have been tested in several hydrogenation reactions with good to excellent performance. Especially, the reduction of N-heterocycles can be performed under very mild conditions.

RESUMEN

Two synthetic approaches have until now been used to synthesize transition metal complexes having a tridentate (pincer or tripod) PEP tetryl (E=Si, Ge, Sn) ligand. These approaches differ in the metal-free precursor, tetrelane or tetrylene, that gives rise to the corresponding PEP tetryl ligand. Tetrelanes (PSiP silanes, PGeP germanes and PSnP stannanes and simple phosphane-free stannanes) have led to tetryl ligands by oxidatively adding an E-X bond (X=H, C or halogen in most cases) to the metal atom of a low-valent transition metal complex, whereas tetrylenes (PGeP germylenes and PSnP stannylenes) have led to tetryl ligands upon insertion of their E atom into an M-X bond (X=Cl in most cases) of the metal precursor or through a derivatization of the E atom after the tetrylene fragment is coordinated to the metal. For each synthetic approach, all the currently known types of PEP tetryl ligand frameworks that have been found in transition metal complexes are presented and discussed in this review.

RESUMEN

The generation of diphosphorus molecules P2 under mild conditions in solution is a useful strategy to generate diphosphines via [4+2] cycloadditions. We recently described the release of P2 units from the nickel butterfly complex [{(IMes)Ni(CO)}2(µ2,η2:η2-P2)] (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) upon addition of CO gas. Herein, we developed an alternative protocol for the same process using heterocumulenes. In addition to formation of P4 (the dimerisation product of P2), the reactions afford nickel complexes of novel pincer-type ligands. Aryl isothiocyanates undergo a trimerisation within the coordination sphere of nickel and afford square planar nickel complexes with S-C-S pincer-ligand frameworks. Carbon disulfide coordinates to the [(IMes)Ni]-fragment in an η2-fashion, affording a dinuclear complex. Similar products are formed when the N-heterocyclic carbene nickel(0) complex [(IMes)Ni(vtms)2] is used as a precursor (vtms=vinyltrimethylsilane).

RESUMEN

The synthesis, characterization and catalytic activity of a new class of diruthenium hydrido carbonyl complexes bound to the tBu PNNP expanded pincer ligand is described. Reacting tBu PNNP with two equiv of RuHCl(PPh3 )3 (CO) at 140 °C produces an insoluble air-stable complex, which was structurally characterized as [Ru2 (tBu PNNP)H(µ-H)Cl(µ-Cl)(CO)2 ] (1) using solid-state NMR, IR and X-ray absorption spectroscopies and follow-up reactivity. A reaction with KOtBu results in deprotonation of a methylene linker to produce [Ru2 (tBu PNNP* )H(µ-H)(µ-OtBu)(CO)2 ] (3) featuring a partially dearomatized naphthyridine core. This enables metal-ligand cooperative activation of H2 analogous to the mononuclear analogue, [Ru(tBu PNP*)H(CO)]. In contrast to the mononuclear system, the bimetallic analogue 3 catalyzes the E-selective semi-hydrogenation of alkynes at ambient temperature and atmospheric H2 pressure with good functional group tolerance. Monitoring the semi-hydrogenation of diphenylacetylene by 1 H NMR spectroscopy shows the intermediacy of Z-stilbene, which is subsequently isomerized to the E-isomer. Initial findings into the mode of action of this system are provided, including the spectroscopic characterization of a polyhydride intermediate and the isolation of a deactivated species with a partially hydrogenated naphthyridine backbone.

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RESUMEN

We report the first examples of metal-promoted double geminal activation of C(sp3 )-H bonds of the N-CH2 -N moiety in an imidazole-type heterocycle, leading to nickel and palladium N-heterocyclic carbene complexes under mild conditions. Reaction of the new electron-rich diphosphine 1,3-bis((di-tert-butylphosphaneyl)methyl)-2,3-dihydro-1H-benzo[d]imidazole (1) with [PdCl2 (cod)] occurred in a stepwise fashion, first by single C-H bond activation yielding the alkyl pincer complex [PdCl(PC sp 3 H P)] (3) with two trans phosphane donors and a covalent Pd-C sp 3 bond. Activation of the C-H bond of the resulting α-methine C sp 3 H-M group occurred subsequently when 3 was treated with HCl to yield the NHC pincer complex [PdCl(PCNHC P)]Cl (2). Treatment of 1 with [NiBr2 (dme)] also afforded a NHC pincer complex, [NiBr(PCNHC P)]Br (6), but the reactions leading to the double geminal C-H bond activation of the N-CH2 -N group were too fast to allow identification or isolation of an intermediate analogous to 3. The determination of six crystal structures, the isolation of reaction intermediates and DFT calculations provided the basis for suggesting the mechanism of the stepwise transformation of a N-CH2 -N moiety in the N-CNHC -N unit of NHC pincer complexes and explain the key differences observed between the Pd and Ni chemistries.

RESUMEN

Carbones are divalent carbon(0) species that contain two lone pairs of electrons. Herein, we have prepared the first known stable and isolable free bis-(carbone) pincer framework with a well-defined solid-state structure. This bis-(carbone) ligand is an effective scaffold for forming monometallic (Ni and Pd) and trinuclear heterometallic complexes with Au-Pd-Au, Au-Ni-Au, and Cu-Ni-Cu configurations. Sophisticated quantum-theoretical analyses found that the metal-metal interactions are too weak to play a significant role in upholding these multi-metallic configurations; rather, the four lone pairs of electrons within the bis-(carbone) framework are the main contributors to the stability of the complexes.

RESUMEN

We report on the reversible uptake of carbon dioxide by dimetallynes featuring ancillary hemi-labile pincer ligands. Insertion into the Ge-Ge/Sn-Sn bonds yields species containing an E(CO2 )E unit, with the mode of ligation of the CO2 fragment determined crystallographically being found to be dependent on the identity of the Group 14 element. The thermodynamics of CO2 uptake/loss can be established through VT NMR (ΔH°=+24.6(2.3) kJ mol-1 , ΔS°=+64.9(3.8) J mol-1 K-1 , ΔG°298 =+5.3(1.9) kJ mol-1 for the loss of CO2 in the Ge case), and the chemical consequences of reversibility demonstrated by thermodynamically-controlled exchange reactions.

RESUMEN

Using a pincer platform based on a bridgehead NHC donor with functional side arms, the combined effect of increased flexibility in six-membered pyrimidine-type heterocycles compared to the more often studied five-membered imidazole, and rigidity of phosphane side arms was examined. The unique features observed include: 1) the reaction of the azolium Csp2 -H bond with [Ni(cod)2 ] affording a carbanionic ligand in [NiCl(PCsp3 H P)] (8) rather than a carbene; 2) its transformation into the NHC, hydrido complex [NiH(PCNHC P)]PF6 (9) upon halide abstraction; 3) ethylene insertion into the Ni-H bond of the latter and ethyl migration to the N-C-N carbon atom of the heterocycle in [Ni(PCEt P)]PF6 (10); and 4) an unprecedented C-P bond activation transforming the P-CNHC -P pincer ligand of 8 in a C-CNHC -P pincer and a terminal phosphanido ligand in [Ni(PPh2 )(CCNHC P)] (15). The data are supported by nine crystal structure determinations and theoretical calculations provided insights into the mechanisms of these transformations, which are relevant to stoichiometric and catalytic steps of general interest.