Reactivity of Oxygen‐Bridged Geminal Al/P and Si/P Frustrated Lewis Pairs towards Heterocumulenes

Autor: Lucas Wickemeyer, Pia C. Trapp, Niklas Aders, Beate Neumann, Hans‐Georg Stammler, Norbert W. Mitzel
Rok vydání: 2023
Předmět:
Zdroj: Chemistry – A European Journal. 29
ISSN: 1521-3765
0947-6539
Popis: The two oxygen-bridged geminal Frustrated Lewis Pairs (FLP) tBu2P-O-AlBis2 (Bis = CH(SiMe3)2, 1) and tBu2P-O-Si(C2F5)3 (2) were reacted with the heterocumulenes PhNCO, PhOCN, PhNCS, CS2 and PhNSO as well as SO2. With isocyanate and cyanate, both 1 and 2, form addition products under formation of five-membered rings. With CS2, isothiocyanate and sulfinylaniline only 1 forms stable adducts, while 2 shows reactivity towards sulfinylaniline but the product decomposed after several minutes. The reaction of 1 with SO2 led to a partial cleavage of the P-O-Al and Al-C units, confirmed by X-ray diffraction studies of a complex aggregate. The reaction of 2 with SO2 affords the 1,2-addition product. All adducts were characterized by means of multinuclear NMR spectroscopy, X-ray crystallography and CHN analyses. © 2023 Wiley-VCH GmbH.
Databáze: OpenAIRE
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