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Main group element catalysts and bond activation reagents

Final Report Summary - MGPCAT (Main group element catalysts and bond activation reagents)

Executive Summary

The Marie Curie project ‘Main group element catalysts and bond activation reagents’ was at the original schedule by mutual agreement between the fellow (Dr Evgeny L Kolychev) and the host (Prof Simon Aldridge), and was undertaken in the Chemistry Research Laboratory, Department of Chemistry, University of Oxford between June 2014 and May 2016. The training acquired by the fellow both in technical/scientific aspects of the project and in more general management, organizational, communication and planning aspects are very important for Dr Kolychev’s scientific career.

Dr Kolychev’s work during his time in Oxford has given rise to four publications to date, including papers in the top-ranking chemistry journals Journal of the American Chemical Society (three) and Chemistry – European Journal (one). One further paper is under consideration currently (with Journal of the American Chemical Society) and three-four more will be submitted in the coming six-month period. In addition, Dr Kolychev was afforded the opportunity to present his work at a number of national and international meetings, including conferences organized by the Royal Society of Chemistry (2016 RSC Coordination and Organometallic Chemistry Discussion Group Meeting, presented poster), IMEBORON 2014 meeting and the 14th International Symposium on Inorganic Ring Systems (IRIS) in Regensburg, Germany (July 2015; presented poster). In addition Dr Kolychev was one of the founder organizing members of the Oxford Chemistry Department’s postdoctoral seminar programme, which has run for the past 12 months. This scheme – which is entirely run by research fellows and post-doctoral associates, invites external speakers in Organometallic and Main Group chemistry, organizes their programme on the day(s) of the visit and is responsible for all logistical aspects of the visits.

Scientifically Dr Kolychev’s output from the project has been prodigious, including the synthesis of novel organic ligands which can be used for the design of diboryl compounds and establishing fundamental bases for creation of chelate diboryl anionic ligands. This work – while fundamental in its nature offers enormous potential going forward in the developing area of main group element coordination compounds with transition metal reactivity in stoichiometric as well as in catalytic conditions. Catalysis is central to wealth creation in modern chemicals/materials manufacture, and the use of new, environmentally friendly and cost-effective catalysts based on main group elements offers a potentially transformative alternative to the continuing use of expensive and toxic heavy transition metal systems.

From a technical perspective, we targeted a number of ligand frameworks for the formation of multi-dentate poly-anionic boryl ligand systems. In particular we targeted Main group element complexes of these ligands as a mechanism for controlling complex geometry and through this approach tune the redox properties of the Main group metal centre. Using this approach redox-based bond modification using these non-typical metals can be targeted – and indeed this is one of the key findings in a recently accepted paper in J. Am. Chem. Soc. to which Dr Kolychev contributed a large amount (J. Am. Chem. Soc., 2016, 138, 4555-4564).

In addition, Dr Kolychev’s work has developed novel procedures for the efficient synthesis of novel dianionic tetra- and penta-dentate ligands which could then be used to prepare bis-boronbromido or boronhydrido species. The use of these species in the formation of related metal complexes is an area of research which is being continued going forward in the host group. Transformation of the bidentate and tridentate ligands to corresponding stannylene complexes and their stoichiometric reactivity to viable catalytic processes has not yet been achieved, but represents one of the major goals of the project going forward, and one which will be enabled by the significant ground work established by Dr Kolychev during the period of the Fellowship.

Additionally a novel and more convenient procedure for the preparation of boryl zinc compounds in one step starting from the boronbromide has been developed. This is potentially ground-breaking, given the difficulty in preparing boryl-metal species directly, and the fact that borylzinc complexes can be utilized directly in a novel bora-Negichi C-B bond forming methodology (manuscript currently under consideration by J. Am. Chem. Soc.).