Pd8(PDip)6: Cubic, Unsaturated, Zerovalent.

Atomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic- as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd8(PDip)6 that is fully characterized by mass spectrometry, heteronuclear and Cross-Polarization Magic-Angle Spinning (CP-MAS) NMR-, infrared (IR), UV-vis, and X-ray photoelectron (XP) spectroscopies, single-crystal X-Ray diffraction (sc-XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104-electron Pd(0) cluster features a cubic Pd8-core, µ4-capping phosphinidene ligands, and is air-stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non-destructive cluster rearrangement as is required for supramolecular assembly.

Insights on the Anion Effect in N-heterocyclic Carbene Based Dinuclear Gold(I) Catalysts.

Dinuclear bisNHC (bis(N-heterocyclic carbene)) gold(I) complexes 3 a and 4 a of general formula [Au2 Br2 (bisNHC)] were tested as catalysts in the cycloisomerization of N-(prop-2-yn-1-yl)benzamide and in the hydromethoxylation of 3-hexyne in the presence of silver(I) activators bearing different counteranions. The catalytic performance of mononuclear NHC complexes (1 a, 2 a) in the same reactions was also studied. The results highlighted the fundamental role of both NHC ligand and counterion in the catalytic cycles and activation process: dinuclear catalysts exhibit higher initial activity even under milder conditions but suffer in terms of stability with respect to mono NHCs. Furthermore, a new dinuclear bisNHC gold(I) complex 4 b of general formula [Au2 (OTs)2 (bisNHC)] (OTs=p-toluenesulfonate) was successfully synthesized and characterized by means of NMR and ESI-MS analyses.

(CAAC)Pd(py) Catalysts Disproportionate to Pd(CAAC)2.

Palladium complexes with one N-heterocyclic carbene (NHC) and a pyridine ancillary ligand are powerful cross-coupling precatalysts. Herein, we report such complexes with a cyclic (alkyl)(amino)carbene (CAAC) ligand replacing the NHC. We find that the alleged reduced form, (CAAC)Pd(py), disproportionates to the (CAAC)2Pd0 complex and palladium nanoparticles. This notwithstanding, they are potent catalysts in the Buchwald-Hartwig amination with aryl chlorides under mild conditions (60 °C). In the presence of dioxygen, these complexes catalyze the formation of diazenes from anilines. The catalytic activities of the NHC- and CAAC-supported palladium(0) and palladium(II) complexes are similar in the cross-coupling reaction, yet the CAAC complexes are superior for diazene formation.

From Au11 to Au13: Tailored Synthesis of Superatomic Di-NHC/PPh3-Stabilized Molecular Gold Nanoclusters.

Herein, we report a new method to synthesize molecular gold nanoclusters (AuNCs) stabilized by phosphine (PR3) and di-N-heterocyclic carbene (di-NHC) ligands. The interaction of di-NHC gold(I) complexes, with the general formula [(di-NHC)Au2Cl2] with well-known [Au11(PPh3)8Cl2]Cl clusters provides three new classes of AuNCs through a controllable reaction sequence. The synthesis involves an initial ligand metathesis reaction to produce [Au11(di-NHC)(PPh3)6Cl2]+ (type 1 clusters), followed by a thermally induced rearrangement/metal complex addition with the formation of Au13 clusters [Au13(di-NHC)2(PPh3)4Cl4]+ (type 2 clusters). Finally, an additional metathesis process yields [Au13(di-NHC)3(PPh3)3Cl3]2+ (type 3 clusters). The electronic and steric properties of the employed di-NHC ligand affect the product distribution, leading to the isolation and full characterization of different clusters as the main product. A type 3 cluster has been also structurally characterized and was preliminarily found to be strongly emissive in solution.

Dinuclear gold(I) Complexes with Bidentate NHC Ligands as Precursors for Alkynyl Complexes via Mechanochemistry.

The use of alkynyl gold(I) complexes covers different research fields, such as bioinorganic chemistry, catalysis, and material science, considering the luminescent properties of the complexes. Regarding this last application, we report here the synthesis of three novel dinuclear gold(I) complexes of the general formula [(diNHC)(Au-C≡CPh)2]: two Au-C≡CPh units are connected by a bridging di(N-heterocyclic carbene) ligand, which should favor the establishment of semi-supported aurophilic interactions. The complexes can be easily synthesized through mechanochemistry upon reacting the pristine dibromido complexes [(diNHC)(AuBr)2] with phenylacetylene and KOH. Interestingly, we were also able to isolate the monosubstituted complex [(diNHC)(Au-C≡CPh)(AuBr)]. The gold(I) species were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. The emission properties were also evaluated, and the salient data are comparable to those of analogous compounds reported in the literature.

Dinuclear gold(I) complexes with N-phosphanyl, N-heterocyclic carbene ligands: synthetic strategies, luminescence properties and anticancer activity.

A small library of dinuclear gold(I) complexes with the title ligands has been prepared, encompassing neutral, mono- and dicationic complexes. The luminescence properties of the complexes in the solid state have been evaluated, and it turns out that neutral and monocationic complexes not presenting a rigid metallamacrocyclic structure can exhibit rather strong emissions that extend towards the red region of the visible spectrum. The in vitro anticancer activity of the complexes has been also preliminarly evaluated; cytotoxicity seems to correlate with complex lipophilicity, whereas selectivity towards cancer cells can be apparently enhanced upon a judicious choice of the ligands.

Synthesis and Biological Studies on Dinuclear Gold(I) Complexes with Di-(N-Heterocyclic Carbene) Ligands Functionalized with Carbohydrates.

The design of novel metal complexes with N-heterocyclic carbene (NHC) ligands that display biological activity is an active research field in organometallic chemistry. One of the possible approaches consists of the use of NHC ligands functionalized with a carbohydrate moiety. Two novel Au(I)-Au(I) dinuclear complexes were synthesized; they present a neutral structure with one bridging diNHC ligand, having one or both heterocyclic rings decorated with a carbohydrate functionality. With the symmetric diNHC ligand, the dicationic dinuclear complex bearing two bridging diNHC ligands was also synthesized. The study was completed by analyzing the antiproliferative properties of these complexes, which were compared to the activity displayed by similar mononuclear Au(I) complexes and by the analogous bimetallic Au(I)-Au(I) complex not functionalized with carbohydrates.

Cross-Linked Polymers as Scaffolds for the Low-Temperature Preparation of Nanostructured Metal Oxides.

The current state of the art of the use of cross-linked organic polymers, both insoluble (resins or gels) and soluble (micro- and nanogels), as aids for the low-temperature preparation of stable metal oxide nanoparticles or nanostructured metal oxides is reviewed herein. Synthetic strategies for inorganic oxide nanomaterials of this kind can greatly benefit from the use of cross-linked polymers, which may act as scaffolds/exotemplates during inorganic nanoparticle synthesis, or as stabilizers following post-synthetic modification of the nanoparticles. Furthermore, the peculiar properties of the organic cross-linked polymers add to those of the inorganic oxide nanoparticles, producing materials with combined properties. The potential applications of such highly promising composite nanomaterials will be also briefly sketched.

Pd Metal Catalysts for Cross-Couplings and Related Reactions in the 21st Century: A Critical Review.

Cross-couplings and related reactions are a class of highly efficient synthetic protocols that are generally promoted by molecular Pd species as catalysts. However, catalysts based on more or less highly dispersed Pd metal have been also employed for this purpose, and their use, which was largely limited to the Heck reaction until the turn of the century, has been extended in recent years to most reactions of this class. This review provides a critical overview on these recent applications of Pd metal catalysts. Particular attention is devoted to the discussion of the mechanistic pathways that have been proposed to explain the catalytic role of Pd metal. Furthermore, the most outstanding Pd metal based catalytic systems that have emerged are illustrated, together with the development of novel approaches to boost the reactivity of Pd metal. A section summarizing the current industrial applications of Pd metal catalyzed reactions of this kind concludes the review.

Palladium(II) Complexes with N-Phosphanyl-N-heterocyclic Carbenes as Catalysts for Intermolecular Alkyne Hydroaminations.

The catalytic potential of palladium(II) complexes with chelating N-phosphanyl-N-heterocyclic carbenes featuring a saturated imidazolin-2-ylidene or tetrahydropyrimid-2-ylidene ring has been investigated in intermolecular alkyne hydroamination reactions. The complexes were found to be among the most active Pd-based catalysts for these processes and to enable the use of low reaction temperatures (40 °C) and of solventless conditions. The Pd complexes require activation by 2 equiv of a silver salt to remove chlorido ligands from the metal coordination sphere; they can however also be presynthesized in active form, which allows their use under silver-free conditions. The hydroamination reaction was found to efficiently proceed with terminal alkynes and different ring-substituted, primary arylamine substrates.

Advances in Transition-Metal-Catalysed Alkyne Hydroarylations.

We present herein a personal account of our achievements in the development of novel catalytic systems based on late-transition-metal complexes for the hydroarylation of alkynes. In particular, our targets were intermolecular hydroarylation reactions with arene or heteroarene substrates devoid of directing groups. We have shown that complexes of palladium, platinum or gold with N-heterocyclic carbene (NHC) ligands can be particularly useful catalysts for this reaction; the NHC ligand imparts greater stability to the complex and renders the catalytic system more productive. Furthermore, we have identified promoters and reaction media that allow to significantly improve the catalytic activity under mild conditions, to control the reaction chemoselectivity and to steer it towards more complex products; thus making this reaction considerably more attractive for the synthetic chemist.

Palladium(II) complexes with chelating N-phosphanyl acyclic diaminocarbenes: synthesis, characterization and catalytic performance in Suzuki couplings.

Complexes of palladium(II) with newly disclosed, N-phosphanyl acyclic diaminocarbene ligands are synthesized for the first time and structurally characterized. The ligands coordinate palladium(II) in a chelating fashion, yielding remarkably stable complexes which can be stored without special precautions in the solid state. Related palladium(II) complexes with an isomerized chelating ligand, formed upon 1,2-migration of the phosphanyl group from the nitrogen to the adjacent carbon atom, have also been isolated in some instances and structurally characterized. The complexes efficiently act as precatalysts for Suzuki coupling reactions of aryl chlorides, where their productivity compares favourably with that of related palladium complexes with acyclic diaminocarbene ligands. In addition, the complexes show a distinct tendency to form as the byproduct the reductive homocoupling product of aryl chloride. This observation, together with ad hoc performed control tests, suggests that Pd colloids are involved in the formation of catalytically competent species.

Correction: Palladium(II) complexes with chelating N-phosphanyl acyclic diaminocarbenes: synthesis, characterization and catalytic performance in Suzuki couplings.

Correction for 'Palladium(ii) complexes with chelating N-phosphanyl acyclic diaminocarbenes: synthesis, characterization and catalytic performance in Suzuki couplings' by Anatoliy Marchenko et al., Dalton Trans., 2016, DOI: 10.1039/c5dt02250a.

Palladium(ii) complexes with electron-poor, 4,5-disubstituted diimidazol-2-ylidene ligands: synthesis, characterization and catalytic activity.

Diimidazolium salts featuring different bridges between the imidazolium groups, as well as electron-withdrawing groups (chloride, cyanide) at the 4- and 5-position of the heterocyclic rings, have been successfully prepared. The diimidazolium salts serve as convenient precursors of di(N-heterocyclic carbene) ligands, which coordinate in a chelating fashion to palladium(ii) centres. The effect of the newly introduced electron-withdrawing groups on the spectroscopic and structural characteristics of the resulting complexes as well as on their reactivity as catalysts in a model alkyne hydroarylation reaction has been investigated and is discussed herein.

Metal nanoparticles inside microgel/clay nanohybrids: Synthesis, characterization and catalytic efficiency in cross-coupling reactions.

HYPOTHESIS: Laponite nanoclay embedded inside soluble crosslinked copolymers (microgels) may act as cation exchanger allowing loading of the microgels with cationic metal precursors, which upon reduction yield tailored ternary colloidal nanocomposites comprising both nanoclay and metal nanoparticles. EXPERIMENTS: Microgel nanohybrids with variable Laponite nanoclay content were loaded with cationic precursors of different noble metals (Pd, Pt, Au); subsequent reduction by several methods yielded ternary nanocomposites which were extensively characterized. Nanocomposites based on Pd were also tested as catalysts in standard Suzuki and Sonogashira cross-coupling reactions. FINDINGS: The proposed method for the production of ternary nanocomposite microgels has been validated. The factors influencing the final metal nanoparticle size (nature of the reducing agent, clay content in the microgel) have been determined and rationalized. The resulting Pd-containing ternary nanocomposite microgels are viable catalysts of standard cross coupling reactions in water-rich medium.

Dinuclear gold(I) complexes with propylene bridged N-heterocyclic dicarbene ligands: synthesis, structures, and trends in reactivities and properties.

Four novel dinuclear N-heterocyclic dicarbene gold(I) complexes with a propylene linker between the carbene moieties have been synthesized and their luminescence and electrochemical properties, together with their reactivity towards bromine oxidative addition, have been screened. All the complexes emit in the solid state in the blue-green spectral range (400-500 nm) with appreciable intensities (Φ(em) up to ≈10%). In cyclic voltammetry, the Au(I)/Au(0) peak splits at low temperature into two separate peaks relative to the couples Au(I)-Au(I)/Au(I)-Au(0) and Au(I)-Au(0)/Au(0)-Au(0), thus indicating the presence of an Au···Au interaction in the dinuclear complex. Oxidative addition of bromine affords as a major or unique product Au(II)-Au(II) complexes most likely as a consequence of the interaction between the two gold centres favoured by the propylene linker.

Alkyne hydroarylation with Au N-heterocyclic carbene catalysts.

Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC) ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III) complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I) complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II) catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh(3)). Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

Blue-emitting dinuclear N-heterocyclic dicarbene gold(I) complex featuring a nearly unit quantum yield.

Dinuclear N-heterocyclic dicarbene gold(I) complexes of general formula [Au(2)(RIm-Y-ImR)(2)](PF(6))(2) (R = Me, Cy; Y = (CH(2))(1-4), o-xylylene, m-xylylene) have been synthesized and screened for their luminescence properties. All the complexes are weakly emissive in solution whereas in the solid state some of them show significant luminescence intensities. In particular, crystals or powders of the complex with R = Me, Y = (CH(2))(3) exhibit an intense blue emission (λ(max) = 450 nm) with a high quantum yield (Φ(em) = 0.96). The X-ray crystal structure of this complex is characterized by a rather short intramolecular Au···Au distance (3.272 Ǻ). Time dependent density functional theory (TDDFT) calculations have been used to calculate the UV/vis properties of the ground state as well as of the first excited state of the complex, the latter featuring a significantly shorter Au···Au distance.

Physical forms of MIPs.

The current state of the art in the development of methodologies for the preparation of MIPs in predetermined physical forms is critically reviewed, with particular attention being paid to the forms most widely employed in practical applications, such as spherical beads in the micro- to nanometer range, microgels, monoliths, membranes. Although applications of the various MIP physical forms are mentioned, the focus of the paper is mainly on the description of the various preparative methods. The aim is to provide the reader with an overview of the latest achievements in the field, as well as with a mean for critically evaluating the various proposed methodologies towards an envisaged application. The review covers the literature up to early 2010, with special emphasis on the developments of the last 10 years.

Alkyne hydroarylation in ionic liquids catalyzed by palladium(II) complexes.

The efficiency of dicarbene palladium(II) complexes and of simple palladium(II) acetate as catalysts for alkyne hydroarylation under liquid-liquid biphasic conditions involving an ionic liquid as the catalyst-containing phase is investigated. The results obtained under these conditions, both in terms of activity and selectivity, are compared with those previously obtained under homogeneous conditions. The catalytic efficiency of the systems is found to be markedly dependent on the nature of the anion of the ionic liquid. Suitable anions are found to significantly improve the catalytic performance in comparison to homogeneous conditions. Preliminary investigations on the recyclability of the system as well as the on advantages of using an acidic ionic liquid are also carried out.