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Title: Cationic rhodium complexes with chelating phosphine and phosphine alkene ligands. Application in dehydrogenation and dehydrocoupling reactions
Author: Dallanegra, Romaeo
ISNI:       0000 0004 2716 5403
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2011
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A series of cationic Rh(I) diphosphine and phosphine-alkene complexes have been isolated and fully characterised. The reactivity of these species towards hydrogenation, dehydrogenation and dehydrocoupling reactions has been investigated. The use of potentially hemilabile ligands DPEphos and XANTphos in the intramolecular dehydrogenation chemistry of tricyclopentylphosphine is reported. The comparison in reactivity of these isolated diphosphine phosphine-alkene complexes towards hydrogenation and with acetonitrile is discussed along with their ability to dehydrocouple secondary silane, Ph₂SiH₂, and amine-borane H₃B·NMe₂H. The acceptorless dehydrogenation of a tethered cyclopentane with cationic Rh(I) diphosphine complexes has also been extended to include thioethers. Isolated cationic Rh(I) phosphine-alkene complexes with labile fluorobenzene ligands are found to act as a source of the reactive 12-electron [Rh{PR₂(ƞ²-C₅H₇)}]+ (R = cyclopentyl (Cyp)/ iPr) fragment in solution and can coordinate two amine-borane ligands (either H₃B·NMe₃, H₃B·NMe₂H or H₃B·NMeH₂) in a novel and unique bis-σ-binding mode. The catalytic activity of some of these isolated complexes in the dehydrocoupling of H₃B·NMe₂H and H₃B·NMeH₂ has been determined. With a view to further understanding the mechanism of catalytic transition metal assisted amine-borane dehydrogenation and dehydrocoupling, known B-N intermediates H₃B·NMe₂BH₂·NMe₂H and [H₂B·NMeH]₃ were also coordinated to the [Rh{PCyp₂(ƞ²-C₅H₇)}]+ fragment and investigated with regard to their role in the catalytic cycle. Structure activity relationships determined from stoichiometric reactions of cationic Rh(I) diphosphine fluorobenzene complexes with amine-boranes enabled the design of a highly efficient homogeneous catalyst capable of dehydrogenating H₃B·NMe₂H to [H₂BNMe₂]₂ at 0.2 mol% loading in 30 minutes at 298 K. Rapid dehydrogenation and dehydrocoupling of H₃B·NMeH₂ to form high molecular weight poly(N-methylaminoborane) with a low PDI has also been achieved. Investigations using model aminoborane H₂B=NiPr₂ and intermediate B-N species H₃B·NMe₂BH₂·NMe₂H and [H₂B·NMeH]₃ has helped establish an overall mechanistic rationale for this process.
Supervisor: Weller, Andrew S. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Inorganic chemistry ; Catalysis ; Organometallic Chemistry ; rhodium ; reaction mechanisms ; catalysis ; phosphine-alkene ; dehydrogenation ; dehydrocoupling ; amine-boranes