Diverse Reactivity of an Electrophilic Phosphasilene towards Anionic Nucleophiles: Substitution or Metal–Amino Exchange |
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Authors: | M?Sc Philipp Willmes M?Sc Lukas Junk Dr Volker Huch Dr Cem B Yildiz Prof?Dr David Scheschkewitz |
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Institution: | 1. Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universit?t des Saarlandes, Saarbrücken, Germany;2. Department of Chemistry, Faculty of Science and Letters, Aksaray University, Aksaray, Turkey |
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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, R2Si=Si(R)Li ( 1 ), apparently proceeds via an initial nucleophilic substitution step as well (as suggested by DFT calculations), but affords a saturated bicyclo1.1.0]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. |
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Keywords: | bicyclic compounds electrophiles phosphasilenes phosphorus silicon |
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