title: Diverse Reactivity of an Electrophilic Phosphasilene towards Anionic Nucleophiles: Substitution or Metal-Amino Exchange.
abstract: The reaction of MesLi (Mes=2,4,6-trimethylphenyl) with the electrophilic phosphasilene R2 (NMe2 )Si-RSi=PNMe2 (2, R=Tip=2,4,6-triisopropylphenyl) cleanly affords R2 (NMe2 )Si-RSi=PMes and thus provides the first example of a substitution reaction at an unperturbed Si=P bond. In toluene, the reaction of 2 with lithium disilenide, R2 Si=Si(R)Li (1), apparently proceeds via an initial nucleophilic substitution step as well (as suggested by DFT calculations), but affords a saturated bicyclo[1.1.0]butane analogue as the final product, which was further characterized as its Fe(CO)4 complex. In contrast, in 1,2-dimethoxyethane the reaction of 1 with 2 results in an unprecedented metal-amino exchange reaction.
authors: Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universität des Saarlandes, 66125, Saarbrücken, Germany.
authors: Philipp
authors: P
authors: Willmes
authors: Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universität des Saarlandes, 66125, Saarbrücken, Germany.
authors: Lukas
authors: L
authors: Junk
authors: Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universität des Saarlandes, 66125, Saarbrücken, Germany.
authors: Volker
authors: V
authors: Huch
authors: Department of Chemistry, Faculty of Science and Letters, Aksaray University, 68100, Aksaray, Turkey. cemburakyildiz@aksaray.edu.tr.
authors: Cem B
authors: CB
authors: Yildiz
authors: Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universität des Saarlandes, 66125, Saarbrücken, Germany. scheschkewitz@mx.uni-saarland.de.
authors: David
authors: 0000-0001-5600-8034
authors: D
authors: Scheschkewitz
keywords: bicyclic compounds; electrophiles; phosphasilenes; phosphorus; silicon