ESR14 Project

Reactivity and catalytic chemistry of Ge/Si-H bonds at metal centres
Recruting institution: CNRS
Diploma-delivering institutions: UPS, UoY
Thesis co-directors: Mary Grellier (LCC, Toulouse, FR), Jason Lynam and John Slattery (UoY, York, UK)
Secondment host: Johnson Matthey PLC (UK)

Objectives
Coordination chemistry of silicon compounds and their applications in catalysis and materials science have been widely explored, but much less is known for the heavier germanium analogue.[1] We will develop new organometallic germanium-based chemistry with a special focus on germane, germyl and germylene species involved in catalyzed hydrogermanation reactions.[2] We will also explore novel methods for Ge-H bond activation in the outer-coordination sphere of metal complexes using highly electrophilic carbene and vinylidene ligands.[3] Such routes will provide access to complimentary pathways for the synthesis of organogermanium compounds.
Expected Results
1) Synthesis of at least 10 exemplar GeH4-nRn compounds (n = 0-3, R = alkyl, aryl, vinyl); 2) Reactivity of these germanium compounds towards M(L)2H2 (M = Fe, Ru and L = diphosphines) and Ru(H)2(H2)2(PR3)2 to form new σ-germane, germyl and germylene complexes; 3) Demonstration of an outer ligand sphere route for Ge-H bond activation, based on electrophilic carbenes ligands; 4) Catalytic hydrogermination reactions of substituted germanes with alkenes and ketones designed to form new functionalised germanes with a high selectivity ( > 99%) and TON > 500 . 5) Map the changes in σ-delocalization and structure of σ-bond complexes between Si and Ge.

[1] K. A. Smart, Motthes-Martin, Vendier, R. N. Perutz, M. Grellier, S. Sabo-Etienne, Organometallics 2015, 34, 4158 and references therein.
[2] R. N. Perutz and S. Sabo-Etienne, Angew. Chem. Int. Ed.2007, 46, 2578.
[3] D. G Johnson, J. M Lynam, N. S Mistry, J. M Slattery, R. J Thatcher, A. C Whitwood, J. Am. Chem. Soc.2013, 135, 2222.