Boryl- und Borylenkomplexe von Palladium und Platin
Final Report Abstract
The boron-element multiple bond project had significant difficulties, particularly with the preparation of suitable starting materials for halosilane elimination, the stability of the desired products, and their reluctance to react with many reactants. Nevertheless, we were able to fully describe the alkylideneboryl system and its hydrobromination reaction recently. More preliminary reactions with unsaturated molecules and Lewis acids have also recently found success, and we expect further results in this area in the future. The boryl, diboran(4)yl and borylene project, in contrast, fared much better. Some unusual borylene ligands were prepared, including iodoborylenes and highly unsaturated, highly charged borylene complexes. The chemistry of boryl complexes was also furthered during the project, with emphasis being placed on the oxidative addition and reductive elimination of B-B and C-B bonds as they relate to catalysis. Particularly the diboran(4)yl ligand has been built into a very promising line of future research. Both the properties and reactivity of this type of ligand, particularly their reduction, is deserving of much further effort.
Publications
- Unexpected Bonding Mode of the Diboran(4)yl Ligand: Combining the Boryl Motif with a Dative Pt–B Interaction. Angew. Chem. Int. Ed. 2011, 50, 7179–7182
H. Braunschweig, A. Damme, T. Kupfer
(See online at https://dx.doi.org/10.1002/anie.201102593) - trans-[Pt(BCat')Me(PCy3)2]: An Experimental Case Study of Reductive Elimination Processes in Pt-Boryls via Associative Mechanisms. Chem. Eur. J. 2011, 17, 11828–11837
H. Braunschweig, R. Bertermann, P. Brenner, M. Burzler, R. D. Dewhurst, K. Radacki, F. Seeler
(See online at https://dx.doi.org/10.1002/chem.201101823) - B=B and B≡E (E = N and O) Multiple Bonds in the Coordination Sphere of Late Transition Metals. Acc. Chem. Res. 2013, ASAP contents
J. Brand, H. Braunschweig, S. S. Sen
(See online at https://doi.org/10.1021/ar400106u) - Bond-strengthening π backdonation in a transition-metal π-diborene complex. Nature Chem. 2013, 5, 115–121
H. Braunschweig, A. Damme, R. D. Dewhurst, A. Vargas
(See online at https://doi.org/10.1038/nchem.1520) - Maximizing Coordinative and Electronic Unsaturation: Three- Coordinate Dicationic Platinum Complexes. Angew. Chem. Int. Ed. 2013, 52, 2981–2984
H. Braunschweig, P. Brenner, R. D. Dewhurst, J. O. C. Jimenez-Halla, T. Kupfer, D. Rais, K. Uttinger
(See online at https://doi.org/10.1002/anie.201209717) - Thermodynamic Control of Oxidative Addition and Reductive Elimination Processes in cis-Bis(dimethoxyboryl)- bis(tricyclohexylphosphine)platinum(II). Chem. Commun. 2013, 49, 5216–5218
H. Braunschweig, A. Damme
(See online at https://dx.doi.org/10.1039/c3cc41444b)
