Triangles and Squares for a Unique Molecular Crystal Structure: Unsupported Two-Coordinate Lithium Cations and CC Agostic Interactions in Cyclopropyllithium Derivatives
Dr. Quentin Dufrois
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Jean-Claude Daran
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Laure Vendier
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Chiara Dinoi
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Current address: LPCNO INSA, 135 Avenue de Rangueil, 31077 Toulouse Cedex 4, France
Search for more papers by this authorCorresponding Author
Prof. Dr. Michel Etienne
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Quentin Dufrois
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Jean-Claude Daran
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Laure Vendier
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorDr. Chiara Dinoi
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Current address: LPCNO INSA, 135 Avenue de Rangueil, 31077 Toulouse Cedex 4, France
Search for more papers by this authorCorresponding Author
Prof. Dr. Michel Etienne
Laboratoire de Chimie de Coordination du CNRS (LCC), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4, France
Search for more papers by this authorAbstract
Understanding and controlling the aggregation state is germane to alkyllithium chemistry. Lewis base-free alkyllithium compounds normally form tetrahedral tetramers or octahedral hexamers in the solid state with the lithium cations being three-coordinate. We report that the unsupported cyclopropyl derivative 1-(trimethylsilyl)cyclopropyllithium [{μ-c-C(SiMe3)C2H4}Li]4 (1), synthesized by the reduction of 1-(phenylthio)-1-(trimethylsilyl)cyclopropane, crystallizes as a tetramer in the space group I-4 with the two-coordinate lithium atoms forming a square. CC agostic interactions complete the coordination sphere around each lithium. The aggregate is preserved in hydrocarbon solution. Furthermore, CC agostic interactions compete intra- and intermolecularly with Lewis base donation as in the unsaturated dimer of 1-(phenylthio)cyclopropyllithium [Li(thf)2{μ-c-C(SPh)C2H4}2Li (thf)] (3) which is also fully characterized.
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