ICHAC-XI, International Conference on Heteroatom Chemistry Caen (France), 14-19 June 2015 REACTIONS OF Li/Cl PHOSPHINIDENOID COMPLEXES WITH C-S π-SYSTEMS Number (to be inserted by us) Jan Faßbender,a Gregor Schnakenburg,a Arturo Espinosa Ferao,*b and Rainer Streubel*a a Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str.1, 53121 Bonn, Germany. E-mail: [email protected] b Departamento de Química Orgánica, Universidad de Murcia,Campus de Espinardo, 30100 Murcia, Spain; E-mail: [email protected] The poster presents the reaction of two Li/Cl phosphinidenoid complexes 2a,b1 with diphenyl thioketone and N,N’-dimethyl thiourea, respectively, which yielded bicyclic 1,2-thiaphospholane complex 4b2 and alkylidene(thioxo)phosphane complex 6a2, respectively ; NMR and structural data will be provided and discussed. Furthermore, DFT studies provide insight into the reaction pathways and bonding details of possible intermediates such as a thiocarbonyl-phosphane-ylid complex or a thiaphosphirane complex, obtained via cyclisation of the former. 1 a) Özbolat, A.; von Frantzius, G.; Marinas Pérez, J.; Nieger, M.; Streubel, R. Angew. Chem., Int. Ed. Engl. 2007, 46, 9327-9330; b) Streubel, R.; Bode, M.; Marinas Pérez, J.; Schnakenburg, G.; Daniels, J.; Nieger, M.; Jones, P.G. Z. Anorg. Allg. Chem. 2009, 635, 1163-1171; c) Albrecht, C.; Bode, M.; Marinas Pérez, J.; Daniels, J.; Schnakenburg, G.; Streubel, R. Dalton Trans. 2011, 40, 2654–2665; d) Nesterov, V.; Schnakenburg, G.; Espinosa, A.; Streubel, R. Inorg. Chem. 2012, 51, 12343–12349; e) Streubel, R.; Özbolat-Schön, A.; von Frantzius, G.; Lee, H.; Schnakenburg, G.; Gudat, D. Inorg. Chem. 2013, 52, 3313–3325. 2 Streubel, R.; Faßbender, J.; Schnakenburg, G.; Espinosa Ferao, A. Chem. Comm. 2015, submitted.