Addition reactions to the intramolecular mesityl2P–CH2–CH2–B(C6F5)2frustrated Lewis pairElectronic supplementary information (ESI) available: Additional experimental and spectroscopic data. CCDC reference numbers 722646, 722647and 767246–767250. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0dt00015a

Hydroboration of dimesitylvinylphosphine with Piers’ borane [HB(C6F5)2] gives the ethylene-bridged intramolecular frustrated P/B Lewis pair 1. It adds pyridine, tert-butyl isocyanide or pivalonitrile to the strongly electrophilic boron center to yield the respective adducts 5–7. Compound 1undergoes a 1,1-phosphine/borane addition to the terminal nitrogen center of phenyl azide to yield the five-membered heterocycle 8, featuring a pendant –NN–Ph. This can be regarded as a boron-stabilized intermediate of a Staudinger reaction. Benzaldehyde and phenyl isocyanate undergo 1,2-P/B additions of 1to their reactive carbonyl groups to yield the corresponding six-membered heterocycles 9and 10, respectively. The P/B Lewis pair reacts with nitrosobenzene by 1,2-addition to the –NO unit under P–N and O–B bond formation to give the six-membered heterocycle 11. The compounds 5–11were characterized by X-ray crystal structure analyses. [ABSTRACT FROM AUTHOR]