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

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‐...

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Published inChemistry : a European journal Vol. 29; no. 21; pp. e202203685 - n/a
Main Authors Wickemeyer, Lucas, Trapp, Pia C., Aders, Niklas, Neumann, Beate, Stammler, Hans‐Georg, Mitzel, Norbert W.
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 13.04.2023
Subjects
Adducts
aluminium
Aluminum
Chemistry
Crystallography
Cyanates
Decomposition reactions
frustrated Lewis pairs
heterocumulenes
Isocyanates
Magnetic resonance spectroscopy
NMR
NMR spectroscopy
Nuclear magnetic resonance
Oxygen
Silicon
small-molecule activation
Sulfur dioxide
aluminium
silicon
heterocumulenes
small-molecule activation
frustrated Lewis pairs
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Summary: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, whereas 2 shows reactivity towards sulfinylaniline, but the product decomposed after a few minutes. The reaction of 1 with SO2 led to partial cleavage of the P−O−Al and Al−C units, as 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. Frustrated pairs’ different preferences: The geminal oxygen‐bridged frustrated Lewis pairs tBu2P−O−AlBis2 (Bis=CH(SiMe3)2) and tBu2P−O−Si(C2F5)3 show different reactivities towards heterocumulenes (PhNCO, PhOCN, PhNCS, CS2, PhNSO) and sulfur dioxide. Whereas the P−O−Al FLP forms stable adducts with all substrates except for SO2, the P−O−Si FLP does not form adducts with sulfur bound to silicon.
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202203685