Heterol Dianions of Group 14 Elements as Building Blocks for the Synthesis of Polarized Multiply-Bonded Compounds and Bicyclic Carbene Analogues

• Applicant: Professor Dr. Thomas Müller
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2019 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 431534440

• Final Report Year: 2024

Final Report Abstract

As the main focus of this project, we investigated the synthesis potential of potassium salts of sila- and germacyclopentadienediides. In conceptually simple salt metathesis reactions, we reacted these with dihalides of elements from Group 13–15 and studied the basic reactivity of the obtained products. This gave us access to new classes of substances with previously unknown structural motifs and, in some cases, promising reactivity patterns. The synthesis of bis-germylenes as part of a SiGe2 three-membered ring is interesting from a bonding theory perspective. The novel borole and alumole complexes of divalent germanium are of general interest due to their wide range of substituent variations and were made available on a preparative scale through the investigations carried out as part of this project. The preparation of phosphanyl-bridged bicyclic germylenes (phospha-BCHGe's) required careful optimization and adaptation of the reaction conditions, but now this class of nucleophilic germylenes stabilized by homoconjugation is also available for further investigations. The synthesis of cyclic germa- and silavinyl anions (2H-tetrolides) is too new a result for the preparative use of this class of substances to be fully clarified. In contrast, with the germaluminocenes we have already been able to establish a class of substances that shows a multifaceted subsequent chemistry and provides access to highly interesting aluminum/germanium compounds.

Publications

• A germaaluminocene. Chemical Science, 11(11), 2982-2986.
  Albers, Lena; Tholen, Patrik; Schmidtmann, Marc & Müller, Thomas
  
• Trialkylsilyl-Substituted Silole and Germole Dianions as Precursors for Unusual Silicon and Germanium Compounds. Accounts of Chemical Research, 53(2), 532-543.
  Dong, Zhaowen; Albers, Lena & Müller, Thomas
  
• Radicals and Anions of Siloles and Germoles. Chemistry – A European Journal, 27(47), 12063-12068.
  Reinhold, Crispin R. W.; Schmidtmann, Marc; Tumanskii, Boris & Müller, Thomas
  
• Three-membered cyclic digermylenes stabilised by an N-heterocyclic carbene. Chemical Science, 12(18), 6287-6292.
  Dong, Zhaowen; Winkler, Jan Mathis; Schmidtmann, Marc & Müller, Thomas
  
• "The versatile reactivity of germole and silole dianions versus Group 13 dihalides” 16th International Symposium on Inorganic Ring Systems (IRIS 16), Graz 25-29.07.2022.
  T. Müller
  
• A phenyl-substituted germole dianion and its reaction with hafnocene dichloride. Mendeleev Communications, 32(1), 46-48.
  Cramer, Hanna H.; Bührmann, Lukas; Schmidtmann, Marc & Müller, Thomas
  
• “Group 13 Heterole Complexes of Si(II) and Ge(II) vs. Ditrielanylsiloles and - germoles: Sila- and Germacyclopentadienediides and their Reaction with Group 13 Halides” 51st Silicon Symposium 18-20.03.2022.
  L. Bührmann
  
• “Intramolecular Competition in Phospha-BCH-Germylenes: Is Germanium or Phosphorus More Lewis Basic? ” 51st Silicon Symposium 18-20.03.2022.
  M. S. Würdemann
  
• “Phospha-BCH-Germylenes – Synthesis and Reactivity” 16thInternational Symposium on Inorganic Ring Systems (IRIS 16), Graz 25-29.07. 2022.
  M. S. Würdemann
  
• “Unexpected Silole and Germole Complexes of Aluminum” 29th International Conference on Organometallic Chemistry (ICOMC-29) Prague 17-22.07.2022.
  L. Albers
  
• „Siloles and Germole Dianions as Precursors for Unusual Main Group Compounds” 29th International Conference on Organometallic Chemistry (ICOMC-29) Prague 17- 22.07.2022.
  T. Müller
  
• “Phospha-BCH-Germylenes – Synthesis and Reactivity” 23. Norddeutsches Doktorandenkolloquium 05/06.10.2023.
  M. S. Würdemann
  
• “Phospha-BCH-Germylenes – Synthesis and Reactivity” International Conference on Phosphorus, Boron and Silicon PBSi Berlin 22-24.03.2023
  M. S. Würdemann
  
• A Bis(silylene)silole – synthesis, properties and reactivity. Dalton Transactions, 53(25), 10446-10452.
  Liu, Chenghuan; Schmidtmann, Marc & Müller, Thomas
  
• Aluminagerma[5]pyramidanes—Formation and Skeletal Rearrangement. Angewandte Chemie International Edition, 63(19).
  Bührmann, Lukas; Albers, Lena; Beuße, Maximilian; Schmidtmann, Marc & Müller, Thomas
  
• Germaaluminocenes—Masked Heterofulvenes. Angewandte Chemie International Edition, 63(24).
  Geibel, Nadeschda; Bührmann, Lukas; Albers, Lena; Schmidtmann, Marc; Weiz, Alexander & Müller, Thomas
  
• Metal ion-driven formation of 2H-silolides and -germolides. Chemical Communications, 60(80), 11295-11298.
  Liu, Chenghuan; Schmidtmann, Marc & Müller, Thomas
  
• Phospha-bicyclohexene-germylenes exhibiting unexpected reactivity. Chemical Science, 15(35), 14161-14170.
  Würdemann, Marie Sophie; Kühn, Steffen; Bötel, Tobias; Schmidtmann, Marc & Müller, Thomas
  
• “Silole and germole anions substituted with stabilized silylenes” 20th International Symposium on Silicon Chemistry, ISOS-20, Hiroshima 12-17.05.2024.
  C. Liu
  
• “Silole and germole dianions as precursors for unusual main group element compounds” 20th International Symposium on Silicon Chemistry, ISOS-20, Hiroshima 12- 17.05.2024.
  T. Müller
  
• „Germaaluminocene – Masked Heterofulvenes“ 24. Norddeutsches Doktorandenkolloquium 26/27.09.2024.
  N. Geibel