The University of Bath is inviting applications for the following PhD project supervised by Dr David Liptrot in the Department of Chemistry.
Over the last two decades, main group chemistry has been transformed by the recognition that appropriately designed low-valent p-block systems are capable of transition metal-mimetic chemistry such as small molecule activation. Such activations, e.g. of dihydrogen or ethene, generally occur via a mechanism reminiscent of the oxidative addition step intrinsic to much transition metal catalysis. In contrast, reductive elimination steps from main group compounds are far less common. As a result, applications of low-valent main group compounds in catalytic transformations has been, with a few exceptions, isolated to steps that occur without change in oxidation state at the metal centre.
This project focuses on low-valent main group compounds from groups 13 and 14 such as digallenes and distannynes as well as heavy carbene analogues such as alanediyls and stanylenes. Due to the reticence of main group compounds to undergo reductive elimination, synthesis of low-valent main group compounds either relies on access to metal halides in an appropriate oxidation state or the use of powerful reducing agents such as alkali metals. Neither of these approaches is relevant to catalytic transformations, precluding us from exploiting the exciting chemistry of low-valent main group fragments in these areas.
Recent work in our lab has disclosed a new synthetic step which can be used to access low-valent main group compounds without the reliance on traditional reducing agents. Instead, well-defined small molecules are used in the reduction of p-block species to generate main group multiple bonds. This step represents the mechanistic analogue of the reductive elimination upon which almost all transition metal catalysed processes rely. This reaction, therefore, “closes the cycle” for main group catalysis with redox switching.
This PhD project would seek to explore the application of non-traditional reducing agents in p-block chemistry; to benchmark the molecular species accessible using this step; and to investigate the inclusion of such a step in catalytic chemistry mediated by low-valent main group compounds.
Candidate requirements:
Candidates should have attained a 2:1 or 1st Class degree in Chemistry and should have a keen interest in synthetic inorganic chemistry. Whilst prior lab experience in inert atmosphere synthesis would be beneficial, full training will be provided especially in light of the effects of COVID-19 on Masters level projects in the 2020/21 academic year. The project will heavily rely on NMR spectroscopy and x-ray crystallography, and so an awareness of the use of and theory behind these techniques is important but hands-on experience is not essential.
Non-UK applicants will also be required to have met the English language entry requirements of the University of Bath.
Enquiries and applications:
Informal enquiries are welcomed and should be directed to Dr David Liptrot, [Email Address Removed]
Formal applications should be made via the University of Bath’s online application form for a PhD in Chemistry (full-time).
More information about applying for a PhD at Bath may be found on our website.
Anticipated start date: 4 October 2021.
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