Metall-Amidoborane als Wasserstoffspeicher: Untersuchungen aus metallorganischer Sicht

• Applicant: Professor Dr. Sjoerd Harder
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2009 to 2014
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 119110703

• Final Report Year: 2014

Final Report Abstract

In conclusion: by studying the effects of substituents, metals and ligands we could obtain important information on the mechanism of H2-release in metal amidoborane complexes. This scheme has been reproduced by calculation (by a competing group) and is now generally accepted. The research also led to a new, highly efficient, method for the synthesis of metal hydride complexes. This method is now used for example in the synthesis of transition metal hydride complexes. The reversibility of the reaction remains an important goal and should be regarded as a holy grail. The largest surprise was that most metal amidoborane complexes are not stable but immediately eliminate R2N=BH2 species and give clean formation of metal hydride complexes. These unexpected results, however, can be exploited in the synthesis of metal hydride complexes and now forms one our standard methods.

Publications

• Chemical Communications 2009, 3455-3456. Convenient Synthesis and Crystal Structure of a Monomeric Zinc Hydride Complex with a Three-Coordinate Metal Center
  Spielmann, Jan; Piesik, Dirk; Wittkamp, Bernd; Jansen, Georg & Harder, Sjoerd
  
• Chemical Communications 2009, 6934-6936. Synthesis and Structure of a Magnesium–Amidoborane Complex and its Role in Catalytic Formation of a New Bis-Aminoborane Ligand
  Spielmann, Jan; Bolte, Michael & Harder, Sjoerd
  
• Journal of the American Chemical Society 2009, 131, 5064-5065. Hydrogen Elimination in Bulky Calcium Amidoborane Complexes: Isolation of a Calcium Borylamide Complex
  Spielmann, Jan & Harder, Sjoerd
  
• Chem. Eur. J. 2010, 16, 8307-8318. Thermal Decomposition of Mono- and Bimetallic Magnesium Amidoborane Complexes
  Spielmann, Jan; Piesik, Dirk F.‐J. & Harder, Sjoerd
  
• Chem. Comm. 2011, 47, 11945-11947. Unprecendented reactivity of an aluminium hydride complex with ArNH2BH3: nucleophilic substitution versus deprotonation
  Harder, Sjoerd & Spielmann, Jan
  
• Dalton Trans. 2011, 40, 8314-8319. Binuclear Magnesium Amidoborane Complexes: Characterization of a Trinuclear Thermal Decomposition Product
  Spielmann, Jan & Harder, Sjoerd
  
• Chem. Eur. J. 2012, 18, 1984-1991. Calcium Amidoborane Ammine Complexes: Thermal Decomposition of Model Systems
  Harder, Sjoerd; Spielmann, Jan & Tobey, Briac