An investigation into the surface chemistry of supported gold phosphine clusters

This thesis describes the preparation and study of a wide range of supported gold catalysts based on atomically-precise triphenyl phosphine stabilised gold clusters. This selected range of ligand-stabilised gold clusters were prepared in attempt to study the effect of increasing cluster nuclearity on the electronic and catalytic properties of these materials. A novel far-infrared study was conducted on the pure cluster materials in attempt to understand the metal-metal and the metal–ligand vibrations, which was also compared to the simulated spectra for each cluster. The design and activation of these novel catalysts based on gold clusters was discussed and the factors that influence activity were described. A comprehensive photoelectron study of the catalysts was conducted in an attempt to understand the electronic structure of the supported gold clusters and the effect of various activation conditions have on the electronic structure of the gold clusters. A selection of the prepared supported gold catalysts were tested for their catalytic activity for the partial oxidation of styrene and the influence of the several activation conditions on the reactivity of the catalyst is also examined. In collaboration, the application of a selection of ligand-stabilised gold clusters as hydrogen sensors and as catalysts for the photocatalytic generation of hydrogen from ethanol is also investigated

EXPERIMENTAL AND THEORETICAL STUDIES TO DEVELOP SUSTAINABLE METHODS IN HOMOGENEOUS GOLD(I) AND GOLD(III) CATALYSIS

Green processes have become an import topic for Chemistry in the last decade. Gold has been proved to play an important role to replace hazardous material thanks to its non-toxicity and biocompatibility. In this thesis, gold(I) complexes were employed in homogeneous catalysis for the transformations involving the activation of carbon\u2010carbon \u3c0-systems. Great results in term of catalytic activity (TON and TOF) and green parameters (E-factor and EMY) were achieved in the hydration of alkynes in neat conditions using NBu4OTf as the only additive. Volatile organic solvents were replaced with success by green solvents in the Meyer-Schuster rearrangement of 1-phenyl-2-propyn-1-ol and in the cyclization of propargylamide, reaching also better performances. These two studies were corroborated also by computational mechanistic investigations, unraveling the unexpected formation of a gold-oxetene intermediate for the Meyer-Schuster reaction. Unlike gold(I), gold(III)-catalyzed reactions are still in their infancy and the vast majority of reports describe the use of inorganic salts. As done for Au(I), the development of knowledge on Au(III) catalysis and stoichiometric reactions is mandatory. Based on our studies about the hydration of alkynes catlyzed by L-Au-X complexes, a [AuIII-(ppy)-IPr]2+ catalyst was engineered to promote this kind of reaction, while maintaining its stability. Structure, reactivity and catalytic properties have been addressed in this thesis by means of multinuclear solution NMR and computational (DFT) studies, with an important focus for the preequilibrium step. NMR spectroscopy combined with DFT calculation has proved successful for the comprehension of reaction mechanisms and to better understand the chemical structure of the catalytic species, thus allowing the development of sustainable homogeneous gold catalysis

The chemistry of new cyclic phosphorus(III) ligands

A range of new aniline derivatives of tetrakis(hydroxymethyl)phosphonium chloride represented as [P(CH2NHR)4]Cl, where R = phenyl or a substituted phenyl group were synthesised by reacting tetrakis(hydroxymethyl)phosphonium chloride with different aniline precursors in EtOH. Similarly, new phenylenediamine derivatives of tetrakis(hydroxymethyl)phosphonium chloride [P{(CH2NHhRh]Cl, [R = C614, C6H3Me, C6H3COPh, C6H2C414] were synthesised by reacting tetrakis(hydroxymethyl)phosphonium chloride with phenylenediamine precursors. Selected aniline derivatives of tetrakis(hydroxymethyl)phosphonium chloride were reacted with triethylamine in acetone at room temperature to give the corresponding diazaphosphorinane ligands cyclo- {CH2N(R)CH2N(R)CH2-P}-CH2N(H)R , where R = phenyl or a substituted phenyl group. Some of the diazaphosphorinane ligands were reacted with Ru(II), Rh(III), Ir(III) , Pd(lI) and Pt(lI) precursors to form new transition metal complexes... cont'

Gold (I) Tetrathiomolybdate Clusters: Synthesis, Characterization, Computational Studies, and Reactivity With Thiophenol and Selenophenol

This thesis describes the synthesis and reactivity of heterometallic complexes containing medicinally active Au(I) and tetrathiomolybdate, [MoS4]2-. The research is motivated by the idea of multifunctional drugs, which are designed to treat diseases through two or more mechanisms of action. Five clusters of the general form, [MoS4(AuL)2] were prepared: C-1 (L=IPr), C-2 (L=IBzMe), C-3 (L=IMes), C-4 (L=PPh3), and C-5 (L=PEt3). The clusters with NHC ligands, C-1, C-2, and C-3 were prepared for the first time and thoroughly characterized by 1H NMR,13C{1H} NMR, UV-vis, cyclic voltammetry, SCXRD, elemental analysis and mass spectrometry. C-4 and C-5, which were reported previously, were prepared to compare the effect of phosphine and NHC ligands on the cluster reactivity. Percent buried volume (% Vbur) calculations show that the steric bulkiness of the ligands increases in the order, C-5 \u3e C-2 \u3e C-4 \u3e C-3 \u3e C-1. A DFT calculation carried out on C-1 suggests the presence of Au-Mo interactions, which could contribute to stabilization of the clusters in addition to the bridging sulfides. The TDDFT study showed that the lowest energy transitions are primarily υ((Au, S) to Mo) and υ(S to Mo) charge transfer. This is consistent with the experimental UV-vis spectra of all five clusters which have lambda max = 487-491 nm. Clusters C-1 – C-5 were screened for antimicrobial activity by CO-ADD lab at the University of Queensland, Australia. C-2 showed notable activity against one fungal strain, Candida albicans, and C-5 showed notable activity against the gram-positive bacteria, methicillin-resistant Staphylococcus aureus and one fungal strain, Cryptococcus neoformans. The reactivity of [MoS4(AuL)2] clusters with PhSH and PhSeH in DMSO-d6 was investigated as a model for thiol- and selenol nucleophiles present in cysteine and selenocysteine proteins. In general, the clusters react with PhSH to a greater extent than with PhSeH. Cluster C-3 was the most reactive with PhSH and PhSeH but this complex was inactive in antimicrobial cytotoxicity testing. Cluster C-4 was not reactive with PhSH or PhSeH and it was completely inactive in cytotoxicity testing. Additional experiments are proposed as future work to better understand the complex interplay of steric and electronic effects in the [MoS4(AuL)2] clusters

Pentafluorophenyl platinum(II) complexes of PTA and its N-allyl and N-benzyl derivatives: Synthesis, characterization and biological activity

From the well-known 1,3,5-triaza-phosphaadamantane (PTA, 1a), the novel N-allyl and N-benzyl tetrafuoroborate salts 1-allyl-1-azonia-3,5-diaza-7-phosphaadamantane (APTA(BF4), 1b) and 1-benzyl-1-azonia-3,5-diaza-7-phosphaadamantane (BzPTA(BF4), 1c) were obtained. These phosphines were then allowed to react with (Pt(\u3bc-Cl)(C6F5)(tht))2 (tht = tetrahydrothiophene) affording the water soluble Pt(II) complexes trans-(PtCl(C6F5)(PTA)2) (2a) and its bis-cationic congeners trans-(PtCl(C6F5)(APTA)2)(BF4)2 (2b) and trans-(PtCl(C6F5)(BzPTA)2)(BF4)2 (2c). The compounds were fully characterized by multinuclear NMR, ESI-MS, elemental analysis and (for 2a) also by single crystal X-ray diffraction, which proved the trans configuration of the phosphine ligands. Furthermore, in order to evaluate the cytotoxic activities of all complexes the normal human dermal fibroblast (NHDF) cell culture were used. The antineoplastic activity of the investigated compounds was checked against the human lung carcinoma (A549), epithelioid cervix carcinoma (HeLa) and breast adenocarcinoma (MCF-7) cell cultures. Interactions between the complexes and human serum albumin (HSA) using fluorescence spectroscopy and circular dichroism spectroscopy (CD) were also investigated

Gold-based Nanomaterials: Spectroscopy, Microscopy and Applications in Catalysis and Sensing

The birth of nanotechnology era has revolutionized materials science, catalysis and field of optoelectronics. Novel and unique phenomena emerge when material dimensions are reduced to ultra-small size regime and enter nanometre (2-100 nm) realm. Such novel materials are expected to replace bulk materials, offering lower cost of manufacturing and enabling progress in many areas such as solar cell, drug delivery, quantum communication and computing, catalysis and sensing applications. With the progress in nanomaterial synthesis and fabrication, the need for the state-of-art characterization techniques became obvious; such techniques help to establish a complete understanding of the nature and interactions of nanosized materials. In this thesis, the first part focuses on the synthesis of gold and ruthenium clusters, namely Au8, Au9, Au101, Ru3, Ru4 and AuRu3, using the well-established synthetic protocols in the literature. Apart from the standard lab-based characterization techniques such as nuclear magnetic resonance (NMR), UV-visible spectroscopy (UV-vis) and Fourier Transform Infra-red (FTIR), a less explored but useful technique far infra-red (far IR) spectroscopy, available at the Australian Synchrotron (AS), was employed to investigate the vibrational modes in these clusters. Peaks in the experimental far IR spectra were assigned unambiguously to specific vibrations by comparing with the ones generated via DFT calculations with the help of collaborators, group of Professor Gregory Metha, University of Adelaide. For the Au9 cluster, three significant gold core vibrations are observed at 157, 177 and 197 cm-1 in the experimental spectrum. In the case of the Ru3 cluster, only a single ruthenium core vibration is identified within the spectrum, at 150 cm-1 with the calculated force constant, k = 0.33 mdyne/Å. The Ru4 cluster exhibits two metal core vibrations at 153 and 170 cm-1 with force constants of 0.35 and 0.53 mdyne/Å, respectively. Substitution with a gold atom yielding a mixed metal AuRu3 cluster shifts the core transitions toward higher wavenumbers at 177 and 299 cm-1 with an increase in force constants to 0.37 and 1.65 mdyne/Å, respectively. This is attributed to the change in chemical composition and geometry of the metal cluster core. A combination of the DFT calculations and high quality synchrotron-based experimental measurements allowed the full assignment of the key transitions in these clusters. Next, these clusters were fabricated into heterogeneous catalysts by depositing on different metal oxide nanopowders. Synchrotron X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) studies were performed at the Australian Synchrotron and the Photon Factory synchrotron in Japan to investigate the electronic structure of Au8, Au9 and Au101 on TiO2 catalysts. The XPS analysis reveals that “as-deposited” Au8 and Au9 retain some un-aggregated clusters while Au101 show bulk-like gold. These findings are in line with TEM observations, where the aggregates (large particles, > 2 nm) of Au8, Au9 and Au101 are hardly seen under HRTEM. UV-visible diffuse reflectance spectroscopy (UV-vis DRS) studies show the absence of localised surface plasmon resonance (LSPR) peaks in these “as-deposited” clusters, suggesting they are below 2 nm in size. Importantly, the XAS spectrum of “as-deposited” Au9 clusters estimates that 60% of pure, un-aggregated Au9 clusters and 40% of bulk gold in the sample. Upon calcination under O2 and combined O2 and H2 (O2-H2), Au8, Au9 and Au101 clusters form larger nanoparticles (> 2 nm) with the appearance of LSPE peak in UV-vis DR spectra. In addition, majority of the phosphine ligands (that stabilise the gold core) dislodge and form phosphine oxide-like species by interacting with oxygen on the TiO2 surface. The third part focused on testing the catalytic performance of the supported Au8, Au9, Au101, Ru3, Ru4 and AuRu3 clusters on different TiO2, SiO2, ZnO and ZrO2 in benzyl alcohol oxidation. Au101-based catalysts display the highest catalytic activity with a turn-over frequency (TOF) up to 0.69 s-1. The high catalytic activity is attributed to the formation of large Au nanoparticles (> 2 nm) that coincides with the partial removal of capping ligands. Au8 and Au9 clusters which contain NO3- counter anions are found to be inactive in benzyl alcohol oxidation. Further work shows that the presence of NO3- species diminishes the catalytic activity. Monometallic ruthenium clusters, Ru3 and Ru4, are found to be inactive yet the bimetallic AuRu3 clusters are active in benzyl alcohol oxidation, suggesting the synergistic effect between ruthenium and gold metal. Investigation of catalytic testing parameters reveals that tuning selectivity of the product is possible through manipulating the reaction temperature. Finally, a joint experiment with Prof. Wojtek Wlodarski’s group at RMIT, Melbourne was undertaken to test the sensing ability of Au9 clusters for hydrogen detection. Au9 clusters were deposited onto radio-frequency (RF) sputtered WO3 films at two different concentrations; 0.01(S1) and 0.1(S2) mg/mL. It was found that the optimal temperatures for sensor S1 and S2 were 300 °C and 350 °C, respectively. The sensor with lower Au9 concentration (S1) displays a faster response and recovery time, and a higher sensitivity toward H2. HRTEM studies reveal that the sensor S1 contain a significant population of sub-5 nm Au nanoparticles which might be responsible for a faster rate of H2 adsorption and dissociation. The key finding in this study suggest that the addition of catalytic layer such as ultra-small Au9 clusters results in improved sensitivity and dynamic performance (response and recovery time) of H2 sensors. In summary, this thesis demonstrated that cluster-based nanomaterials have wide range of applications spanning from catalysis to sensing. Further improvements in material synthesis and use of multiple complimentary characterization techniques allowed better understanding of the nature of the key active species (metal nanoparticles) assisting design of catalysts and sensors with enhanced performance

Advances in Chemical Crystallography: A Themed Issue Honoring Professor Alexandra M. Z. Slawin on the Occasion of Her 60th Birthday

A compilation of papers presenting original research results in the areas of organic, inorganic, organometallic, solid state and theoretical chemistry with a common theme of the use of X-ray diffraction to solve chemical problems

Dft Study Of Geometry And Energetics Of Transition Metal Systems

This dissertation focuses on computational study of the geometry and energetics small molecules and nanoclusters involving transition metals (TM). These clusters may be used for various industrial applications including catalysis and photonics. Specifically, in this work we have studied hydrides and carbides of 3d-transition metal systems (Sc through Cu), small nickel and gold clusters. Qualitatively correct description of the bond dissociation is ensured by allowing the spatial and spin symmetry to break. We have tested applicability of new exchange-correlation functional and alternative theoretical descriptions (spin-contamination correction in broken symmetry DFT and ensemble Kohn-Sham (EKS)) as well. We studies TM hydrides and carbides systems to understand the importance of underlying phenomenon of bond breaking in catalytic processes. We have tested several exchange-correlation functionals including explicit dependence on kinetic energy density for the description of hydrides (both neutral and cationic) and carbides formed by 3d-transition metals. We find M05-2x and BMK dissociation energies are in better agreement with experiment (where available) than those obtained with high level wavefunction theory methods, published previously. This agreement with experiment deteriorates quickly for other functionals when the fraction of the Hartree-Fock exchange in DFT functional is decreased. Higher fraction of HF exchange is also essential in EKS formalism, but it does not help when spin-adapted unrestricted approach is employed. We analyze the electron spin densities using Natural Bond Orbital population analysis and find that simple description of 3d electrons as non-bonding in character is rarely correct. Unrestricted formalism results in appreciable spin-contamination for some of the systems at equilibrium, which motivated us to investigate it further in details. In order to correct the spin contamination effect on the energies, we propose a new scheme to correct for spin contamination arising in broken-symmetry DFT approach. Unlike conventional schemes, our spin correction is introduced for each spin-polarized electron pair individually and therefore is expected to yield more accurate energy values. We derive an expression to extract the energy of the pure singlet state from the energy of the broken-symmetry DFT description of the low spin state and the energies of the high spin states (pentuplet and two spin-contaminated triplets in the case of two spin-polarized electron pairs). We validate our spin-contamination correction approach by a simple example of H2 and applied to more complex MnH system. Ensemble KS formalism is also applied to investigate the dissociation of C2 molecule. We find that high fraction of HF exchange is essential to reproduce the results of EKS treatment with exact exchange-correlation functional. We analyze the geometry and energetics of small nickel clusters (Ni2-Ni5) for several lowest energy isomers. We also study all possible spin states of small nickel cluster isomers and report observed trends in energetics. Finally we determine the geometry and energetics of ten lowest energy isomers of four small gold clusters (Au2, Au4, Au6, and Au8). We have also investigated the influence of cluster geometry, ligation, solvation and relativistic effects on electronic structure of these gold clusters. The effect of one-by-one ligand attachment in vacuum and solvent environment is also studied. Performance of five DFT functionals are tested as well; Local Spin Density Approximation (SVWN5), Generalized Gradient Approximation (PBE), kinetic energy density-dependent functional (TPSS), hybrid DFT (B3LYP), and CAM-B3LYP which accounts for long-range exchange effects believed to be important in the analysis of metal bonding in gold complexes and clusters. Our results exhibit the ligand induced stability enhancement of otherwise less stable isomers of Au4, Au6 and Au8. Ligands are found to play a crucial role in determining the 2D to 3D transition realized in small gold clusters. In order to select an appropriate theory level to use in this study, we investigate the effect of attachment of four different ligands (NH3, NMe3, PH3, PMe3) on cluster geometry and energetics of Au2 and Au4 in vacuum and in solution. Our results benchmark the applicability of DFT functional model and polarization functions in the basis set for calculations of ligated gold cluster systems. We employ five different basis sets with increasing amount of polarization and diffuse functions; LANL2DZ, LANL2DZ-P, def2-SVP, def2-TZVP, and def2-QZVP. We obtain NMe3 = NH3 \u3e PH3 \u3e PMe3 order of ligand binding energies and observe shallow potential energy surfaces in all molecules. Our results suggest appropriate quantum-chemical methodologies to model small noble metal clusters in realistic ligand environment to provide reliable theoretical analysis in order to complement experiments