Willmes, PhilippJunk, LukasHuch, VolkerYıldız, Cem BurakScheschkewitz, David13.07.20192019-07-2913.07.20192019-07-2920161433-78511521-3773https://doi.org/10.1002/anie.201605699https://hdl.handle.net/20.500.12451/6090The reaction of MesLi (Mes=2,4,6-trimethylphenyl) with the electrophilic phosphasilene R-2(NMe2)Si-RSi=PNMe2 (2, R=Tip=2,4,6-triisopropylphenyl) cleanly affords R-2(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 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.eninfo:eu-repo/semantics/openAccessBicyclic CompoundsElectrophilesPhosphasilenesPhosphorusSiliconArticle5536109131091710.1002/anie.20160569927509901Q1WOS:000383473600074N/A