DEHYDROCOUPLE · Unravelling the Mechanism of Phosphine-Borane Dehydrocoupling for the Synthesis to Order of Valuable New Materials

Unravelling the Mechanism of Phosphine-Borane Dehydrocoupling for the Synthesis to Order of Valuable New Materials

The project has made good progress with the Fellow working hard to achieve a number of key intermediate goals. He has developed the chemistry of a variety of {Rh(PR3)2}+ fragments with a variety of phosphine boranes (primary and secondary) and, through this, made key insights into the likely intermediates in the phosphine borane dehydrocoupling reaction using these fragments. Importantly he has, for the first time, resolved the catalytic species in Manners’ initial report of phosphine–borane dehydrocoupling using the [Rh(COD)2]+ catalysts. This work has been published: Chem. Commun., (2012) 48, 7185-7187. Building upon this the Fellow is now investigating the detailed mechanistic pathway for dehydrocoupling, including for the first time the determination of thermodynamic and kinetic parameters. After this excellent first year, the project was focused in the dehydrocoupling of Ph2HP·BH3, with this phosphine-borane were obtained important results and the Fellow was able to propose a well-defined catalytic cycle for the dehydrocoupling of secondary phosphine-boranes (more details in the Final Report attached as PDF). This work has been published: Chem. Sci., (2013) 4, 1881-1888. The last months, the project was focused in determinate the different rates for this reaction when the phosphine–borane is changed (manuscript in preparation). The good progress in this project has made possible obtain a grant (in collaboration with Ian Manners) to continue working in this area in the Andrew Weller’ group. Training has been received in advanced X-ray crystallography (he now determines structures for himself and others in the group), NMR spectroscopy (including the kinetic analysis of catalytic systems) and advanced Schlenk-line and glove box techniques. He has also been active in the mentoring and development of junior members of the group. He has presented frequently at group meetings: both his own work and literature work. He has also presented his work at a joint meeting with Ian Manners’ group (Bristol) on dehydrocoupling. He was a participant at the major boron (IMEBORON XIV) and organometallic (XXVICOMC) conferences. Resources have been used as in the proposal. There are no significant deviations.

Текст от CORDIS, на английски · Данни: CORDIS, © Европейски съюз