Studies of metal compounds containing carbon chains - approaches to novel materials. There is an increasing need to design functional devices on the molecular scale ("nanotechnology"). We are developing the chemistry of compounds which contain chains of up to 12 carbon atoms to allow electronic communication between metal centres attached to each end. This projects seeks to extend this work, to discover new and more effective compounds, and to develop the associated chemistry to provide synthese ....Studies of metal compounds containing carbon chains - approaches to novel materials. There is an increasing need to design functional devices on the molecular scale ("nanotechnology"). We are developing the chemistry of compounds which contain chains of up to 12 carbon atoms to allow electronic communication between metal centres attached to each end. This projects seeks to extend this work, to discover new and more effective compounds, and to develop the associated chemistry to provide syntheses of novel compounds of potential use in the fine chemicals industry. Extensive collaboration with French colleagues exists and will continue.Read moreRead less
All-carbon molecules in metal complexes - novel materials and intermediates. An important requirement for the future is new materials with unusual properties that can be controlled. The need for ever smaller electronic devices requires knowledge about appropriate properties (particularly electronic) of molecules designed to model devices such as wires, switches, etc. This work seeks to design, measure and evaluate such molecules, which are based on chains of carbon atoms linking metal centres ....All-carbon molecules in metal complexes - novel materials and intermediates. An important requirement for the future is new materials with unusual properties that can be controlled. The need for ever smaller electronic devices requires knowledge about appropriate properties (particularly electronic) of molecules designed to model devices such as wires, switches, etc. This work seeks to design, measure and evaluate such molecules, which are based on chains of carbon atoms linking metal centres which can gain or lose electrons readily. As the electronic structure changes, so do the physical (photo, solid-state) and chemical properties (reactivity). Improved understanding of these features will benefit development of advanced technology and new materials.Read moreRead less
Understanding biological nitrogen fixation: an investigation of multi-electron reduction catalysis at novel iron-sulfur clusters. A new class of iron-sulfur clusters held together by a central light atom will be prepared and their reactions thoroughly studied. These clusters are important because they will have the same structure as the iron-molybdenum cluster of the enzyme nitrogenase. This enzyme fixes atmospheric nitrogen as ammonia. It is the primary route of nitrogen entry into all living s ....Understanding biological nitrogen fixation: an investigation of multi-electron reduction catalysis at novel iron-sulfur clusters. A new class of iron-sulfur clusters held together by a central light atom will be prepared and their reactions thoroughly studied. These clusters are important because they will have the same structure as the iron-molybdenum cluster of the enzyme nitrogenase. This enzyme fixes atmospheric nitrogen as ammonia. It is the primary route of nitrogen entry into all living systems. Industrially ammonia is produced in an energy-demanding process on a vast scale. The studies will provide insights into how nitrogenase works and how to design new multi-electron reduction catalysts. The research may lead to new energy-efficient routes to ammonia and to other new alternative fuel sources. Such processes would transform Australian industry and how we live.Read moreRead less
Asymmetric Synthesis of Chiral Phosphines, Arsines, and Stibines. There are now chiral phosphine-transition metal catalysts that rival enzymes in their efficiency for the asymmetric synthesis of important chiral drugs, fragrants, cosmetics, nutrients, vitamins, and pesticides. This project is aimed at a generalised asymmetric synthesis of the critical components of these enzyme mimics, notably enantiopure chiral phosphines, but also chiral arsines and stibines, by a highly innovative approach t ....Asymmetric Synthesis of Chiral Phosphines, Arsines, and Stibines. There are now chiral phosphine-transition metal catalysts that rival enzymes in their efficiency for the asymmetric synthesis of important chiral drugs, fragrants, cosmetics, nutrients, vitamins, and pesticides. This project is aimed at a generalised asymmetric synthesis of the critical components of these enzyme mimics, notably enantiopure chiral phosphines, but also chiral arsines and stibines, by a highly innovative approach that involves novel six-electron phosphenium, arsenium, and stibinium cations that are themselves stabilised by chiral phosphines so that chemical breeder reactions are possible. The use of chiral auxiliaries from the natural pool and from biotechnology will also be investigated.Read moreRead less
Towards Nano-circuits: 2 and 3-Dimensional Carbon-Wired Nano-architectures. Whilst Australia has a world-class profile in organotransition metal chemistry, main-group chemistry is under-represented, despite the enormous technological importance of materials based on these elements. In addition to the fundamental breakthrough science to be explored, the project will provide a training vehicle for 5 young scientists in both main group and organometallic chemistry. The target compounds involve an e ....Towards Nano-circuits: 2 and 3-Dimensional Carbon-Wired Nano-architectures. Whilst Australia has a world-class profile in organotransition metal chemistry, main-group chemistry is under-represented, despite the enormous technological importance of materials based on these elements. In addition to the fundamental breakthrough science to be explored, the project will provide a training vehicle for 5 young scientists in both main group and organometallic chemistry. The target compounds involve an essentially unique marriage of the fields of main-group and transition metal chemistry to provide complex nano-architectures based on the modular interconnection of metals and non-metals by carbon wires at the molecular level - nanoscopic counterparts of macroscopic circuit components.Read moreRead less
Understanding and Harnessing the Unique and Curious Metal Boron Bond: Unlocking the Metallaboratrane Cage. Metal-boron bonding holds enormous technological importance due to the emergence of boron-based metal-mediated synthetic transformations that access a diversity of high value-added fine chemicals. Whilst Australia boasts an emergent boron-based fine chemicals industry, no research program into the nature of metal boron bonding exists to provide either fundamental science or advanced trainin ....Understanding and Harnessing the Unique and Curious Metal Boron Bond: Unlocking the Metallaboratrane Cage. Metal-boron bonding holds enormous technological importance due to the emergence of boron-based metal-mediated synthetic transformations that access a diversity of high value-added fine chemicals. Whilst Australia boasts an emergent boron-based fine chemicals industry, no research program into the nature of metal boron bonding exists to provide either fundamental science or advanced training in organometallic boron chemistry. The proposed work offers two distinct national benefits: The maintenance of a discipline in which Australia leads the world (metallaboratranes) and the genesis of one, which whilst intensely studied elsewhere, is notably absent from the Australian science base (low coordinate, unsaturated boron chemistry).Read moreRead less
Reactions of Coordinated Dinitrogen. The program will develop novel metal-based catalysts and reagents that will transform nitrogen gas into ammonia and other nitrogen-containing compounds (nitrogen fixation). This fundamental chemical transformation underpins major chemical industries and this new approach using organometallic catalysts will significantly improve the efficiency of ammonia production and reduce the energy and harsh reaction conditions currently required. This program will desi ....Reactions of Coordinated Dinitrogen. The program will develop novel metal-based catalysts and reagents that will transform nitrogen gas into ammonia and other nitrogen-containing compounds (nitrogen fixation). This fundamental chemical transformation underpins major chemical industries and this new approach using organometallic catalysts will significantly improve the efficiency of ammonia production and reduce the energy and harsh reaction conditions currently required. This program will design catalysts with multiple complementary metal centres tailored to bind and activate nitrogen gas to facilitate its reaction with hydrogen or other reagents.Read moreRead less
A new metalloprotein-inspired methodology for energy-efficient chemical reduction. Chemical reduction, a core process in chemistry and industry, is carried out on an enormous scale using present-day technology that is extremely energy wasteful and irreversibly consumes resources. This project aims to provide a new sustainable methodology for chemical reduction using sophisticated bio-inspired metal (electro) catalysts.
Redox initiated chemistry of hydrogenase H-cluster model compounds: Biologically inspired hydrogen activation catalysts? High efficiency, low temperature, cheap hydrogen activation catalysts suitable for fuel cell applications would provide the basis for the development of environmentally benign technologies suitable for transportation and some power applications. Hydrogenase enzymes are high efficiency, low temperature, hydrogen activation catalysts and the active site of the all-iron version ....Redox initiated chemistry of hydrogenase H-cluster model compounds: Biologically inspired hydrogen activation catalysts? High efficiency, low temperature, cheap hydrogen activation catalysts suitable for fuel cell applications would provide the basis for the development of environmentally benign technologies suitable for transportation and some power applications. Hydrogenase enzymes are high efficiency, low temperature, hydrogen activation catalysts and the active site of the all-iron version of the enzyme has recently been revealed to be a remarkable, weakly protein bound, iron-sulfur-carbonyl-cyanide complex. Research into the reactions of redox activated abiological model compounds will provide insights into the molecular basis of the enzymatic reaction, potentially leading to the discovery of highly efficient, biologically inspired hydrogen activation catalysts.Read moreRead less
Metal-promoted bond functionalisation: new routes to amides and thioamides. This project aims to discover new metal-promoted methods to synthesise amides and thioamides, important structural motifs in chemistry and biology. The project will use a mechanism-based approach that integrates theory with gas- and solution-phase experiments to discover new chemical reactions. A benefit of this research will be new eco-friendly alternatives to existing processes, thereby reducing waste and eliminating t ....Metal-promoted bond functionalisation: new routes to amides and thioamides. This project aims to discover new metal-promoted methods to synthesise amides and thioamides, important structural motifs in chemistry and biology. The project will use a mechanism-based approach that integrates theory with gas- and solution-phase experiments to discover new chemical reactions. A benefit of this research will be new eco-friendly alternatives to existing processes, thereby reducing waste and eliminating toxic and expensive reagents.Read moreRead less