Dynamic Metal-to-Element Dative Bonds and their Applications Beyond the Molecule

• Applicant: Professor Dr. Holger Braunschweig
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2010 to 2019
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 192178519

• Final Report Year: 2019

Final Report Abstract

Overall, the results of this funding period constitute a considerable extension of the previous work, and allowed a more holistic picture of the behaviour of MOLPs, especially those with Lewis base groups based on Group 8 and 10 metals. Attempts were made to push the boundaries of MOLP chemistry by (a) increasing topicity of the acid and base units, (b) extending acids to the lighter Group 15 elements, (c) using Lewis acid transfer experiments as a gauge of Lewis basicity, and (d) using the results of these transfer experiments to guide catalysis with Group 8 Lewis bases. Most of this work was included in comprehensive full papers, which detailed the fascinating ability of indium trihalides to establish equilibria between their MOLP and OA products with Pt0 species.

Publications

• Lewis Acid Binding and Transfer as a Versatile Experimental Gauge of the Lewis Basicity of Fe0, Ru0 and Pt0 Complexes. Chem. Eur. J. 2015, 21, 19195–19201
  H. Braunschweig, C. Brunecker, R. D. Dewhurst, C. Schneider, B. Wennemann
  
• Dynamic, Reversible Oxidative Addition of Highly Polar Bonds to a Transition Metal. J. Am. Chem. Soc. 2016, 138, 16140–16147
  R. Bertermann, J. Böhnke, H. Braunschweig, R. D. Dewhurst, T. Kupfer, J. H. Müssig, L. Pentecost, K. Radacki, S. S. Sen, A. Vargas
  
• Metal-Only Lewis Pairs Based on Zerovalent Osmium. Organometallics 2016, 35, 2567–2573
  R. Bissert, H. Braunschweig, R. D. Dewhurst, C. Schneider
  
• Steric Control between Neutral Metal-Only Lewis Pairs and Metal-Stabilized Gallenium and Gallinium Cations. Organometallics 2016, 35, 1002–1007
  H. Braunschweig, R. D. Dewhurst, C. Schneider
  
• Formation of a Trifluorophosphane Platinum(II) Complex by P—F Bond Activation of Phosphorus Pentafluoride with a Pt(0) Complex. Chem. Eur. J. 2017, 23, 5948–5952
  N. Arnold, R. Bertermann, F. M. Bickelhaupt, H. Braunschweig, M. Drisch, M. Finze, F. Hupp, J. Poater, J. A. P. Sprenger
  
• Does Lewis basicity correlate with catalytic activity in zerovalent group 8 complexes? Z. Naturforsch. 2018, 73b, 149–153
  H. Braunschweig, C. Brunecker, R. D. Dewhurst, C. Schneider
  
• Reactions of Digallanes with p- and d-Block Lewis Bases: Adducts, Bis(gallyl) Complexes and Naked Ga+ as Ligand. Chem. Eur. J. 2018, 24, 9692–9697
  J. K. Schuster, J. H. Müssig, R. D. Dewhurst, H. Braunschweig
  
• Oxidative addition of arsenic halides to platinum(0). Dalton Trans. 2019, 48, 3547–3550
  J. H. Müssig, T. E. Stennett, U. Schmidt, R. D. Dewhurst, L. Mailänder, H. Braunschweig