Carbonylation Reactions of Intramolecular Vicinal Frustrated Phosphane/Borane Lewis Pairs

The intramolecular frustrated Lewis pair (FLP) Mes2PCH2CH2B­(C6F5)2 4 adds cooperatively to carbon monoxide to form the five-membered heterocyclic carbonyl compound 5. The intramolecular FLP 7 contains an exo-3-B­(C6F5)2 Lewis acid and an endo-2-PMes2 Lewis base functionality coordinated at the norbornane framework. This noninteracting FLP adds carbon monoxide in solution at −35 °C cooperatively to yield a five-membered heterocyclic FLP-carbonyl compound 8. In contrast, FLP 7 is carbonylated in a CO-doped argon matrix at 25 K to selectively form a borane carbonyl 9 without involvement of the adjacent phosphanyl moiety. The free FLP 7 was generated in the gas phase from its FLPH2 product 10. A DFT study has shown that the phosphonium hydrido borate zwitterion 10 is formed exergonically in solution but tends to lose H2 when brought into the gas phase.