Silica‐Supported Zirconium Complexes and their Polyoligosilsesquioxane Analogues in the Transesterification of Acrylates: Part 1. Synthesis and Characterization

Various silica‐supported acetylacetonate and alkoxy zirconium(IV) complexes have been prepared and characterized by quantitative chemical measurements of the surface reaction products, quantitative surface microanalysis of the surface complexes, in situ infrared spectroscopy, CP‐MAS ¹³C NMR spectroscopy and EXAFS. The complex (SiO)Zr(acac)₃ (acac=acetylacetonate ligand) ( 1 ) can be obtained by reaction of zirconium tetraacetylacetonate [Zr(acac)₄] with a silica surface previously dehydroxylated at 500 °C. The complexes (SiO)₃Zr(acac) ( 2 ) and (SiO)₃Zr(O‐n‐Bu) (n‐Bu=butyl ligand) ( 3 ) can be synthesized by reaction of (SiO)₃Zr H with, respectively, acetylacetone and n‐butanol at room temperature. The spectroscopic data, including EXAFS spectroscopy, confirm that in compound 1 the zirconium is linked to the surface by only one Si O Zr bond whereas in the case of compounds 2 and 3 the zirconium is linked to 3 surface oxygen atoms which are sigma bonded. EXAFS data indicate also that the acetylacetonate ligands behave as chelating ligands leading to a hepta‐coordination around the zirconium atom in 1 and a penta‐coordination in 2 . In order to provide a molecular analogue of 1 , the synthesis of the following polyoligosilsesquioxane derivative (c‐C₅H₉)₇Si₈O₁₂(CH₃)₂Zr(acac)₃ ( 1′ ) was achieved. The compound 1′ is obtained by reacting (c‐C₅H₉)₇Si₈O₁₁(CH₃)₂(OH), 4 , with an equimolecular amount of Zr(acac)₄. In the same manner, syntheses of complexes (c‐C₅H₉)₇Si₇O₁₂Zr(acac) ( 2′ ) and of (c‐C₅H₉)₇Si₇O₁₂Zr(O‐n‐Bu) ( 3′ ) were achieved by reaction of the unmodified trisilanol, (c‐C₅H₉)₇Si₇O₉(OH)₃, with respectively Zr(acac)₄ and Zr(O‐n‐Bu)₄ at 60 °C in tetrahydrofuran. Compounds 1′ , 2′ and 3′ can be considered as good models of 1 , 2 and 3 since their spectroscopic properties are comparable with those of the surface complexes. The synthetic results obtained will permit us to study the catalytic properties of these surface complexes and of their molecular analogues with the ultimate goal of delineating clear structure‐activity relationships.     

A well-defined supported metal catalyst: Ir4/MgO

[Ir₄(CO)₁₂] was used as a precursor for the preparation of a MgO-supported catalyst with a uniquely simple metal structure, Ir₄. The precursor was adsorbed on MgO from hexanes with the metal framework remaining intact, as determined by extended X-ray absorption fine structure (EXAFS) spectra. The surface-bound species was inferred to be predominantly [HIr₄(CO)₁₁]^–, which could be extracted from the surface by cation metathesis and identified in solution by infrared spectroscopy. After treatment of the MgO-supported iridium carbonyl in He followed by H₂ at 300 °C, the sample was characterized again by EXAFS spectroscopy; the results provide evidence that the predominant surface species are clusters of four Ir atoms with an average Ir-Ir distance of 2.69 Å.     

Catalytic hydroboration of vinylarenes using a zwitterionic arylspiroboronate ester iridium complex

Addition of B₂cat₃ (cat = 1,2-O₂C₆H₄) to Ir(acac)(dppb) (1; where dppb = 1,4-bis(diphenylphosphino)butane) gave the novel arylspiroboronate ester iridium complex Ir(η⁶-catBcat)(dppb) (2), the first example of an iridium compound containing a coordinating [Bcat₂]^? anion. Complex 2 is a remarkably selective catalyst precursor for the hydroboration of unhindered vinylarenes using pinacolborane.     

Synthesis,characterization, and application for addition polymerization of norbornene of novel acetylacetonate bis(anilines) palladium (II) complexes

New acetylacetonate bis(aniline) palladium (II) complexes were synthesized by nitrile substitution of [Pd(acac)(MeCN)₂]BF₄ with L (L = o-toluidine, p-toluidine, 2,6-dimethylaniline, 2,6-diisopropylaniline) which yielded [Pd(acac)(L)₂]BF₄ as a mononuclear species with chelating acac ligand. Preliminary investigations into the polymerization of norbornene in the presence of BF₃·OEt₂ were performed. An X-ray diffraction study of [Pd(acac){NH₂(2,6-Me₂C₆H₃)}₂]BF₄ establishes the presence of hydrogen bonding between the 2,6-dimethylaniline ligand and [BF₄]⁻ anion.     

Novel yellow phosphorescent iridium complexes containing a carbazole–oxadiazole unit used in polymeric light-emitting diodes

Yellow iridium complexes Ir(PPOHC)₃ and (PPOHC)₂Ir(acac) (PPOHC: 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole) were synthesized and characterized. The Ir(PPOHC)₃ complex has good thermal stability with 5% weight-reduction occurring at 370 °C and a glass-transition temperature of 201 °C. A polymeric light-emitting diode using the Ir(PPOHC)₃ complex as a phosphorescent dopant showed a luminance efficiency of 16.4 cd/A and the maximum external quantum efficiency of 6.6% with CIE coordinates of (0.50, 0.49). A white polymeric light-emitting diode was fabricated using Ir(PPOHC)₃ which showed a luminance efficiency of 15.3 cd/A, with CIE coordinates of (0.39, 0.44). These results indicate that the iridium complexes containing a linked carbazole–oxadiazole unit are promising candidates in high-efficiency electroluminescent devices.     

Novel yellow phosphorescent iridium complexes containing a carbazole-oxadiazole unit used in polymeric light-emitting diodes

Yellow iridium complexes Ir(PPOHC)₃ and (PPOHC)₂Ir(acac) (PPOHC: 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole) were synthesized and characterized. The Ir(PPOHC)₃ complex has good thermal stability with 5% weight-reduction occurring at 370 °C and a glass-transition temperature of 201 °C. A polymeric light-emitting diode using the Ir(PPOHC)₃ complex as a phosphorescent dopant showed a luminance efficiency of 16.4 cd/A and the maximum external quantum efficiency of 6.6% with CIE coordinates of (0.50, 0.49). A white polymeric light-emitting diode was fabricated using Ir(PPOHC)₃ which showed a luminance efficiency of 15.3 cd/A, with CIE coordinates of (0.39, 0.44). These results indicate that the iridium complexes containing a linked carbazole-oxadiazole unit are promising candidates in high-efficiency electroluminescent devices.     

Supported iridium catalysts prepared by atomic layer deposition: effect of reduction and calcination on activity in toluene hydrogenation

Ligand removal from supported iridium catalysts prepared by atomic layer deposition from Ir(acac)₃ was studied by direct reduction in hydrogen flow and by calcination in oxygen flow followed by reduction in hydrogen flow, as well as by thermogravimetric analysis. Thermal decomposition of acac ligand residuals required high temperatures, and in samples containing no iridium the removal of carbonaceous species was not complete. Metallic iridium particles less than 2 nm in size were formed during direct reduction and larger particles upon calcination followed by reduction. The activity of the catalysts in toluene hydrogenation in most cases depended on particle size.     

Hydrogenation of nitriles with iridium-triphenylphosphine complexes

Reactions of cationic iridium(I)-COD (COD = 1,5-cyclooctadiene) complexes, [Ir(COD)(PhCN)(PPh₃)]ClO₄ (1), [Ir(COD)(PPh₃)₂]ClO₄ (2) and [Ir(COD)(PhCN)₂]ClO₄ (3) with nitriles under H₂ catalytically produce primary, secondary and tertiary amines. Hydrogenation of nitriles (RCN) gives HCl salts of amines (RCH₂NH₂HCl, (RCH₂)₂NH HCl) in CH₂Cl₂. Secondary and tertiary amines seem to be produced by the reactions of RCN with primary and secondary amines, respectively under H₂ in the presence of catalysts. The hydrogenation in the presence of1 and2 is homogeneously catalyzed by soluble iridium-PPh₃ complexes formed in the reactions of1 and2 with H₂ and RCN whereas the hydrogenation in the presence of3 is heterogeneous by metallic iridium powders produced in the reduction of3 by H₂.     

Formation of Gold Clusters on TiO2 from Adsorbed Au(CH3)2(C5H7O2): Characterization by X-ray Absorption Spectroscopy

Gold nanoclusters on TiO₂ powder were prepared from adsorbed Au^III(CH₃)₂(C₅H₇O₂) (dimethyl acetylacetonate gold(III)) and characterized by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies. The samples were tested as catalysts for CO oxidation at 298 K and atmospheric pressure and characterized by EXAFS and XANES with the catalysts in the working state. The XANES results identify Au(III) in the initially prepared sample, and the EXAFS data indicate mononuclear gold complexes as the predominant surface gold species in this sample, consistent with the lack of Au–Au contributions in the EXAFS spectrum. The mononuclear gold complex is bonded to two oxygen atoms of the TiO₂ surface at an Au–O distance of 2.16 Å. Treatment of this complex in He or in H₂ at increasing temperatures led to formation of metallic gold clusters of increasing size, ultimately those with an average diameter of about 15 Å. The data demonstrate the presence of metallic gold clusters in the working catalysts and also show these clusters alone are not responsible for the catalytic activity.     

EXAFS characterization of supported metal-complex and metal-cluster catalysts made from organometallic precursors

Nearly uniform (nearly molecular) supported metals made from molecular organometallic precursors are ideally suited to characterization by EXAFS spectroscopy at the metal edge. Among the most thoroughly investigated mononuclear metal complexes on metal oxide and zeolite supports are MgO-supported rhenium subcarbonyls, approximately Re(CO)₃{OMg}₃ (where the braces denote groups terminating the bulk of the support). These were made, e.g., from [HRe(CO)⁵] and from [H₃Re₃(CO)₁₂]; the Re–O_surface distance determined by EXAFS spectroscopy is 2.15 ± 0.03 Å the support is a tridentate ligand. The Re–O_surface distances in related supported complexes of Groups 7 and 8 metals are all in the range of 2.1–2.2 Å, matching those in molecular analogues. HTa{OSi}₂, prepared from [Ta(CH₂C(CH₃)₃)₃(=CHCCH₃)₃] on SiO₂, catalyzes a new reaction, propane metathesis. Supported complexes made from [HRe(CO)⁵] catalyze alkene hydrogenation but not cyclopropane hydrogenolysis, whereas catalysts made from [H₃Re₃(CO)₁₂] catalyze both these reactions, and EXAFS data indicate neighboring Re centers on the latter (but not the former), which are implicated in the catalysis. EXAFS data similarly indicate supported Mo and W pair sites as catalysts. Supported metal clusters made by decarbonylation of metal carbonyl clusters, e.g., Ir₄/γ-Al₂O₃ and Ir₆/γ-Al₂O₃ or Rh₆/zeolite NaY, are indicated by EXAFS data to be tetrahedra and octahedra, respectively. Such clusters are the species detected by EXAFS spectroscopy at 298 K in the presence of propene and H₂ undergoing catalytic hydrogenation, and they are identified as the catalytically active species. The catalytic activities of the clusters for toluene hydrogenation and alkene hydrogenation are almost unaffected by changes in metal oxide support composition, but they depend on the cluster size, although the catalytic reaction is structure insensitive. Thus, supported metal clusters offer new catalytic properties.     

Silica‐Supported Zirconium Complexes and their Polyoligosilsesquioxane Analogues in the Transesterification of Acrylates: Part 2. Activity,Recycling and Regeneration

The catalytic activity of both supported and soluble molecular zirconium complexes was studied in the transesterification reaction of ethyl acrylate by butanol. Two series of catalysts were employed: three well defined silica‐supported acetylacetonate and n‐butoxy zirconium(IV) complexes linked to the surface by one or three siloxane bonds, (SiO)Zr(acac)₃ ( 1 ) (SiO)₃Zr(acac) ( 2 ) and (SiO)₃Zr(O‐n‐Bu) ( 3 ), and their soluble polyoligosilsesquioxy analogues (c‐C₅H₉)₇Si₈O₁₂(CH₃)₂Zr(acac)₃ ( 1′ ), (c‐C₅H₉)₇Si₇O₁₂Zr(acac) ( 2′ ), and (c‐C₅H₉)₇Si₇O₁₂Zr(O‐n‐Bu) (3′ ). The reactivity of these complexes were compared to relevant molecular catalysts [zirconium tetraacetylacetonate, Zr(acac)₄ and zirconium tetra‐n‐butoxide, Zr(O‐n‐Bu)₄]. Strong activity relationships between the silica‐supported complexes and their polyoligosilsesquioxane analogues were established. Acetylacetonate complexes were found to be far superior to alkoxide complexes. The monopodal complexes 1 and 1′ were found to be the most active in their respective series. Studies on the recycling of the heterogeneous catalysts showed significant degradation of activity for the acetylacetonate complexes ( 1 and 2 ) but not for the less active tripodal alkoxide catalyst, 3 . Two factors are thought to contribute to the deactivation of catalyst: the lixivation of zirconium by cleavage of surface siloxide bonds and exchange reactions between acetylacetonate ligands and alcohols in the substrate/product solution. It was shown that the addition of acetylacetone to the low activity catalyst Zr(O‐n‐Bu)₄ produced a system that was as active as Zr(acac)₄. The applicability of ligand addition to heterogeneous systems was then studied. The addition of acetylacetone to the low activity solid catalyst 3 produced a highly active catalyst and the addition of a stoichiometric quantity of acetylacetone at each successive batch catalytic run greatly reduced catalyst deactivation for the highly active catalyst 1 .     

Cyclometallated iridium(III) complexes with dicyanamide or tricyanomethanide

Reaction of cyclometallated iridium(III) complex Ir(ppy)₂(PPh₃)Cl (2, ppy = 2-phenylpyridine) with dicyanamide or tricyanomethanide gave neutral mononuclear complexes Ir(ppy)₂(PPh₃)N(CN)₂ (3a) or Ir(ppy)₂(PPh₃)C(CN)₃ (3b), and dicyanamide/tricyanomethanide-linked binuclear iridium(III) complexes [{Ir(ppy)₂(PPh₃)}₂N(CN)₂]⁺ (4a) or [{Ir(ppy)₂(PPh₃)}₂C(CN)₃]⁺ (4b). Substitution of coordinated chloride in the precursor 2 with dicyanamide or tricyanomethanide improved significantly the luminescence properties of 3a–4b. Compared with that in the precursor 2 (1.6%), 2.2 to 9.3-fold enhancement of emission quantum yields was detected in 3a–4b.     

Hexairidium carbonyl clusters in the micropores of faujasite zeolites: evidence from transmission electron microscopy

[Ir₆(CO)₁₆] was formed in the pores of zeolite NaY by adsorption of [Ir(CO)₂(acac)] followed by treatment in CO + H₂. [Ir₆(CO)₁₅]²⁻ in zeolite NaX was prepared similarly. Each sample was characterized by high‐resolution transmission electron microscopy. The images indicate the presence of the iridium clusters in the zeolite micropores, with almost no scattering centers indicating iridium outside these pores. The supported [Ir₆(CO)₁₆] and [Ir₆(CO)₁₅]²⁻, which have previously been characterized by infrared and extended X‐ray absorption fine structure spectroscopies, are among the most uniform and structurally best defined supported metal clusters. This revised version was published online in July 2006 with corrections to the Cover Date.     

PAMAM Dendrimer-Derived Ir/Al2O3 Catalysts: An EXAFS Characterization

Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to characterize several synthesis stages of hydroxyl-terminated generation four (G4OH) PAMAM dendrimer-derived Ir/γ-Al₂O₃ catalyst. The EXAFS results indicate that Ir³⁺ forms complexes with dendrimer functional groups through displacement of two Cl^? ion ligands. These complexes are very stable in solution, and no reduction of Ir³⁺ to Ir nanoparticles or clusters is observed after introduction of reducing agents such as NaBH₄ or H₂. These Ir³⁺-dendrimer complexes remain essentially intact after support impregnation. The formation of 1–2 nm particles occurs when the catalysts are treated with O₂/H₂ or H₂, and the dendrimer-derived catalysts exhibit a lower degree of metal support interaction.     

The synthesis and single-crystal X-ray structure of the first mononuclear iridium carbonyl hydride with two orthometallated phosphite ligands,cis-[IrHCO{P(O-o-tBuC6H3) (O-o-tBuC6H4)2}2]

[Ir(μ-OMe)(COD)]₂ reacts with tris-ortho-tert-butylphenylphosphite in the presence of carbon monoxide to give the first example of a mononuclear iridium carbonyl hydride complex with two orthometallated phosphite ligands cis-[IrHCO{P(O-o-^tBuC₆H₃) (O-o-^tBuC₆H₄)₂}₂]. The complex shows great stability even under high pressures of hydrogen and carbon monoxide.     

A Comparative Analysis of the In Vitro Anticancer Activity of Iridium(III) {η5-C5Me4R} Complexes with Variable R Groups

Piano-stool iridium complexes based on the pentamethylcyclopentadienyl ligand (Cp*) have been intensively investigated as anticancer drug candidates and hold much promise in this setting. A systematic study aimed at outlining the effect of Cp* mono-derivatization on the antiproliferative activity is presented here. Thus, the dinuclear complexes [Ir(η⁵-C₅Me₄R)Cl(μ-Cl)]₂ (R = Me, 1a; R = H, 1b; R = Pr, 1c; R = 4-C₆H₄F, 1d; R = 4-C₆H₄OH, 1e), their 2-phenylpyridyl mononuclear derivatives [Ir(η⁵-C₅Me₄R)(k_N,k_CPhPy)Cl] (2a–d), and the dimethylsulfoxide complex [Ir{η⁵-C₅Me₄(4-C₆H₄OH)}Cl₂(κ_S-Me₂S=O)] (3) were synthesized, structurally characterized, and assessed for their cytotoxicity towards a panel of six human and rodent cancer cell lines (mouse melanoma, B16; rat glioma, C6; breast adenocarcinoma, MCF-7; colorectal carcinoma, SW620 and HCT116; ovarian carcinoma, A2780) and one primary, human fetal lung fibroblast cell line (MRC5). Complexes 2b (R = H) and 2d (4-C₆H₄F) emerged as the most active ones and were selected for further investigation. They did not affect the viability of primary mouse peritoneal cells, and their tumoricidal action arises from the combined influence on cellular proliferation, apoptosis and senescence. The latter is triggered by mitochondrial failure and production of reactive oxygen and nitrogen species.     

Effect of reductants in N2O reduction over Fe-MFI catalysts

We investigated the effect of reductants over ion-exchanged Fe-MFI catalysts (Fe-MFI) based on the catalytic performance in N₂O reduction in the presence and absence of an oxygen atmosphere. In the case of N₂O reduction with hydrocarbons (CH₄, C₂H₆, and C₃H₆) in the presence of excess oxygen, the order of N₂O contribution was as follows: CH₄ > C₂H₆ > C₃H₆. This indicates that CH₄ is a more efficient reductant than C₂H₆ and C₃H₆. The TOFs of N₂O decomposition and the N₂O reduction by various reductants (H₂, CO, CH₄) in the absence of oxygen increased with increasing Fe/Al ratio (Fe/Al⩾0.15), wheras the TOFs were lower and constant in the range of Fe/Al⩽0.10. Temperature-programmed reduction with hydrogen (H₂-TPR) showed that the catalysts with a higher Fe/Al ratio were reduced more easily than those with a lower Fe/Al ratio. Temperature-programmed desorption of O₂ (O₂-TPD) showed that oxygen was desorbed at lower temperatures over the catalysts with a higher Fe/Al ratio. As the result of extended X-ray absorption fine structure (EXAFS) analysis, only mononuclear Fe species were observed over Fe(0.10)-MFI after treatment with N₂O or O₂. On the other hand, binuclear Fe species and mononuclear Fe species were observed over Fe(0.40)-MFI after treatment with N₂O or H₂. More reducible Fe species, which gave lower-temperature O₂ desorption, can be due to Fe binuclear species. Since the N₂O reduction with reductants proceeds via a redox mechanism, the reducible binuclear Fe species can exhibit higher activity. Furthermore, CH₄ can be oxidized by N₂O more easily than can H₂ and CO, although it is generally known that the reactivity of methane is very low.     

SCR of NO over Ir/Al2O3 Catalysts. Importance of the Activation Procedure and Influence of the Dispersion

For SCR of NO the study of Ir/Al₂O₃ solids shows the importance of the activation procedure under mixtures containing CO (NO–C₃H₆–CO–O₂ or NO–CO–O₂). The selective reductant remains C₃H₆, however. The activation goes with an iridium particles sintering without Ir loss.     

Properties of Magnesium Oxo-Fluoride Supports for Metal Catalysts

A mixed MgF₂–MgO system has been tested as a potential support of iridium catalysts in the hydrodesulfurization of thiophene. Samples of MgF₂–MgO with different contents of MgO (0–100%) have been prepared by one-step sol–gel method in the reaction of magnesium methoxide dissolved in methanol with hydrofluoric acid. They have been used as supports for the synthesis of iridium (1 wt% Ir) catalysts. The supports have been characterized by XRD, low temperature nitrogen adsorption and thermogravimetric measurements. The one-step method of MgF₂–MgO synthesis has been shown to permit the control of MgO content in the mixed system. The MgF₂–MgO samples are classified as mesoporous, of large surface area (100–450 m² g^?1) depending on the amount of MgO introduced, with the maximum for 71 mol% MgO. The presence of two phases in the mixture delays the process of both MgF₂ and MgO crystallization and increases the resistance of the MgF₂–MgO texture to treatment at temperatures up to 800 °C. The catalysts obtained by deposition of the iridium phase on MgF₂, MgO and MgF₂–MgO (62 mol% MgO) calcined at 400–700 °C, have been tested in the reaction of hydrodesulfurization of thiophene. The most active has been the iridium catalyst supported on MgF₂–MgO.     

A convenient one-step synthesis of alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III)

Alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) were prepared by reactions of [(p-cymene)RuCl₂(PPh₃)] or [C_p^*MCl₂(PPh₃)] (M=Rh, Ir; C_p^*=C₅Me₅) with 1-ethynylbenzene and triphenylphosphine in the presence of KPF₆.