N-Heterocyclic Carbene Coordinated Neutral and Cationic Heavier Cyclopropylidenes†
Dr. Anukul Jana
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Current address: Tata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brundavan Colony, Narsingi, Hyderabad-500075 (India)
Search for more papers by this authorDipl.-Chem. Isabell Omlor
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Search for more papers by this authorDr. Volker Huch
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Search for more papers by this authorProf. Dr. Henry S. Rzepa
Department of Chemistry, Imperial College London, London SW7 2AZ (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. David Scheschkewitz
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.htmlSearch for more papers by this authorDr. Anukul Jana
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Current address: Tata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brundavan Colony, Narsingi, Hyderabad-500075 (India)
Search for more papers by this authorDipl.-Chem. Isabell Omlor
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Search for more papers by this authorDr. Volker Huch
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Search for more papers by this authorProf. Dr. Henry S. Rzepa
Department of Chemistry, Imperial College London, London SW7 2AZ (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. David Scheschkewitz
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.htmlSearch for more papers by this authorSupport by the EPSRC (EP/H048804/1), the COST Action CM1302 (Smart Inorganic Polymers), and the Alfried Krupp von Bohlen und Halbach Foundation is gratefully acknowledged.
Graphical Abstract
He is heavy and he′s my brother: NHC-coordinated cyclopropenylidene analogues with molecular scaffolds exclusively formed by heavier Group 14 elements are accessible from the corresponding vinylidene isomers by exchange of the NHC ligand for a smaller NHC. The residual chloride in one of these heavier cyclic carbenes can be expelled by a second equivalent of NHC to generate cationic derivatives of the imidazolium type.
Abstract
Cyclopropylidene is a transient intermediate of the allene–propyne–cyclopropene isomerization. The incorporation of heavier Group 14 elements into the cyclopropylidene scaffold has to date been restricted to the formal replacement of the carbenic carbon atom by a base-coordinated silicon(II) center. Herein we report the synthesis and characterization of NHC-coordinated heavier cyclopropylidenes (Si2GeR3X, and Si3R3Br; X=Cl, Mes; R=Tip=2,4,6-iPr3C6H2) in which the three-membered ring is exclusively formed by silicon and germanium. In case of the chloro-substituted Si2Ge-cyclopropylidene, a stable heavier cycloprop-1-yl-2-ylidene cation is obtained by NHC-induced chloride dissociation.
Supporting Information
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