Tuning Pd-to-Ag Ratio to Enhance the Synergistic Activity of Fly Ash-Supported PdxAgy Bimetallic Nanoparticles.

Fly ash (FA)-supported bimetallic nanoparticles (PdxAgy/FA) with varying Pd:Ag ratios were prepared by coprecipitation of Pd and Ag involving in situ reduction of Pd(II) and Ag(I) salts in aqueous medium. All the supported nanoparticles were thoroughly characterized with the aid of powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), electron microscopy (field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM)), and elemental analyses, which include inductively coupled plasma-optical emission spectroscopy (ICP-OES) and energy-dispersive X-ray spectroscopy (EDS). A gradual broadening and shifting of PXRD peaks, ascribable to Ag, to higher angles with an increase in the Pd:Ag ratio affirms the alloying of interface between Pd and Ag nanoparticles. The coexistence of Pd and Ag was further confirmed by EDS elemental mapping as well as by the presence of bimetallic lattices on the FA surface, as evident from the high-resolution TEM analysis. The dependency of crystallite size and average size of bimetallic nanoparticles on Ag loading (mol %) was elucidated with the help of a combination of PXRD and TEM studies. Based on XPS analysis, the charge transfer phenomenon between contacting Pd-Ag sites could be evident from the shifting of 3d core electron binding energy for both Pd and Ag compared with monometallic Pd and Ag nanoparticles. Following a pseudo-first-order reaction kinetics, all the nanocatalysts were able to efficiently reduce 4-nitrophenol into 4-aminophenol in aqueous NaBH4. The superior catalytic performance of the bimetallic nanocatalysts (PdxAgy/FA) over their monometallic (Pd100/FA and Ag100/FA) analogues has been demonstrated. Moreover, the tunable synergistic effect of the bimetallic systems has been explored in detail by varying the Pd:Ag mol ratio in a systematic manner which in turn allowed us to achieve an optimum reaction rate (k = 1.050 min-1) for the nitrophenol reduction using a Pd25Ag75/FA system. Most importantly, all the bimetallic nanocatalysts explored here exhibited excellent normalized rate constants (K ≈ 6000-15,000 min-1 mmol-1) compared with other supported bimetallic Pd-Ag nanocatalysts reported in the literature.

Unveiling meta-Alkyloxy/-Silyloxy-Substituted N-Aryl PNP Ligands for Efficient Cr-Catalyzed Ethylene Tetramerization.

Novel N-aryl-functionalized PNP ligands (1-4) bearing m-alkyloxy/-silyloxy substituents were prepared and evaluated for chromium-catalyzed ethylene oligomerization using MMAO-3A as an activator. The selected Cr/PNP system under optimized condition exhibited high 1-octene-selective (up to 70 wt %) ethylene tetramerization at a remarkable rate (over 3000 kg gCr-1 h-1). More importantly, the undesirable polyethylene selectivity was restricted to a minimum level of ∼1-2 wt % for pre-catalysts derived with ligands 1 and 2. Employing chlorobenzene as a reaction medium yielded best productivity in conjunction to the total α-olefin (1-C6 + 1-C8) selectivity (∼88 wt %). N-aryl PNP ligands (3 and 4) incorporating m-silyloxy substituents in the phenyl ring exhibited relatively poorer tetramerization performance while yielding higher PE fraction as compared to their m-alkyloxy derivatives. A detailed molecular structure of the best-performing pre-catalyst 1-Cr was established by single-crystal X-ray diffraction analysis. The stability of 1/Cr-based catalyst system was investigated for a reaction time of up to 2 h under optimized condition.

A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality.

Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)3/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg gCr-1 h-1) and C8 olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C6 + 1-C8) selectivities, exceeding 90 wt%, as a result of high 1-C6 purity (>90 wt%) in the C6 fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C6 cyclics controlled highly α-selective ethylene oligomerization.

Highly Efficient Ethylene Tetramerization Using Cr Catalysts Constructed with Trifluoromethyl-Substituted N-Aryl PNP Ligands.

Tetramerization of ethylene by chromium catalysts stabilized with functionalized N-aryl phosphineamine ligands C6H4(m-CF3)N(PPh2)2 (1), C6H4(p-CF3)N(PPh2)2 (2), C6H4(o-CF3)N=PPh2-PPh2 (3), and C6H3(3,5-bis(CF3))N(PPh2)2 (4) was evaluated. The parameter optimization includes temperature, co-catalyst, and solvent. Upon activation with MMAO-3A, the new catalyst system especially with m-functional PNP ligand (1) exhibited high 1-octene selectivity and productivity while giving minimum undesirable polyethylene and C10 + olefin by-products. Using PhCl as a solvent at 75 °C led to a remarkable α-olefin (1-C6 + 1-C8) selectivity (>90 wt %) at a reaction rate of 2000 kg·gCr -1·h-1. Under identical conditions, analogous PNP ligands bearing -CH3, -Et, and -Cl functional moieties at the meta position of the N-phenyl ring displayed significantly lower reactivity. The catalyst with p-functional ligand (2) exhibited lower activity and comparable selectivities, while the Cr/PPN (with ligand 3) system gave no noticeable reactivity. The molecular structure of the precatalyst (1-Cr), exhibiting a monomeric structural feature, was elucidated with the aid of single-crystal X-ray diffraction study.

Clean chlorination of silica surfaces by a single-site substitution approach.

A chlorination method for the selective substitution of well-defined isolated silanol groups of the silica surface has been developed using the catalytic Appel reaction. Spectroscopic analysis, complemented by elemental microanalysis studies, reveals that a quantitative chlorination could be achieved with highly dehydroxylated silica materials that exclusively possess non-hydrogen bonded silanol groups. The employed method did not leave any carbon or phosphorus residue on the silica surface and can be regarded as a promising tool for the future functionalization of metal oxide surfaces.

SOMC grafting of vanadium oxytriisopropoxide (VO(O i Pr)3) on dehydroxylated silica; analysis of surface complexes and thermal restructuring mechanism.

Vanadium oxytriisopropoxide (VO(O i Pr)3), 1, was grafted on highly dehydroxylated silica (SiO2-700: aerosil silica treated at 700 °C under high vacuum) to generate compound 2 following the concepts and methodology of surface organometallic chemistry (SOMC). The resulting compound was analyzed by elemental analysis, FT-IR, 1H, 13C and 51V solid state (SS) NMR, Raman and EPR spectroscopies. The grafting reaction of 1 to generate 2 was found to lead to the formation of a monopodal surface complex [([triple bond, length as m-dash]Si-O-)V(O)(O i Pr)2], 2m, as well as bipodal [([triple bond, length as m-dash]Si-O-)2V(O)(O i Pr)], 2b, formed along with ([triple bond, length as m-dash]Si-O- i Pr) moieties as an effect of the classical rearrangement of 2m with strained siloxane bridges. Upon controlled thermal treatment at 200 °C under high vacuum, 2m and 2b were found to mainly rearrange to tetrahedral VO4 moieties [([triple bond, length as m-dash]Si-O-)3V(O)] (3) with formation of propylene whereas the ([triple bond, length as m-dash]Si-O- i Pr) groups were preserved. The mechanism of the thermal rearrangement of the isopropoxide groups was investigated by a DFT approach revealing the occurrence of a concerted γ-H-transfer and olefin elimination mechanism.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts.

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon.

A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH2+ ) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2 ) and the µ-iminodiborane (-µ-NHB2 H5 ) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.

Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst.

The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH2tBu)3 was selectively prepared by grafting of MoO(CH2tBu)3Cl onto partially dehydroxylated silica (silica700) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO3/SiO2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions.

Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides.

The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si-O-)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si-O-)WH3(Me)2], as the predominant species at -78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si-O-)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

Triptycene based luminescent metal-organic gels for chemosensing.

We report a novel luminescent Al-based metal-organic gel G1 comprising 1,4,5,8-triptycenetetracarboxylic acid, which exhibits highly sensitive detection towards nitro aromatic compounds particularly picric acid. Furthermore, under identical reaction conditions, using a Co(II) salt instead, a novel 3D framework material, trip-MOF-1, was isolated and its sensitivity towards picric acid was also evaluated.

Incorporation of active metal sites in MOFs via in situ generated ligand deficient metal-linker complexes.

Two novel 3D MOFs, namely MOF-647A and MOF-648 (previously unknown trinodal 4-connected net), comprised of Cu ions and pyrazole-3,5-dicarboxylate were synthesized and characterized. A strategy for incorporating open metal sites in MOFs was investigated by utilizing an in situ generated metal-linker complex as a precursor to construct MOF-648.

Azulene based metal-organic frameworks for strong adsorption of H2.

Two Zn MOFs, MOF-645 and MOF-646, comprised of polarized 1,3-azulenedicarboxylate were synthesized. The guest free MOF-646 showed strong MOF-H(2) interactions (7.8-6.8 kJ mol(-1)), which revealed the significant impact of internally polarized azulene backbone to stabilized H(2) molecules in the framework.

Highly convenient amine-free sonogashira coupling in air in a polar mixed aqueous medium by trans- and cis-[(NHC)2PdX2] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes.

Two new trans- and cis-[(NHC)(2)PdX(2)] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes employed in a highly convenient amine-free Sonogashira cross-coupling reaction in air in a polar mixed aqueous medium are reported. Specifically, the trans-[{1-benzyl-3-(3,3-dimethyl-2-oxobutyl)imidazol-2-ylidene}(2)PdBr(2)] (3) and cis-[{1-benzyl-3-(N-tert-butylacetamido)imidazol-2-ylidene}(2)PdCl(2)] (4) complexes effectively catalyzed the Sonogashira cross-coupling reaction of aryl iodides with substituted acetylenes in air in a mixed solvent (DMF/H(2)O, 3:1 v/v) under amine-free conditions. Interestingly, these trans- and cis-[(NHC)(2)PdX(2)] (X=Cl, Br) complexes, with two N-heterocyclic carbene ligands, exhibited superior activity compared with the now popular PEPPSI (pyridine enhanced precatalyst preparation, stabilization and initiation)-themed analogues, trans-[(NHC)Pd(pyridine)X(2)] (X=Cl, Br), 3 a and 4 a, with one N-heterocyclic carbene ligand and a "throw away" pyridine ligand in a trans disposition to each other. The higher activities of 3 and 4 compared with PEPPSI analogues 3 a and 4 a are attributed to more-electron-rich metal centers, as revealed by DFT studies, in the former complexes and is in concurrence with a more electron-rich metal center being effective in facilitating the oxidative addition of aryl halide, often a rate-determining step in palladium-mediated cross-coupling reactions. Complexes 3 and 4 were prepared from the corresponding silver analogues by transmetalation with [(cod)PdCl(2)], whereas the corresponding PEPPSI analogues 3 a and 4 a were obtained directly from the imidazolium halide salts by reaction with PdCl(2) in pyridine in the presence of K(2)CO(3) as base.