Cascade chemistry in azacryptand cages: bridging carbonates and methylcarbonates

Dussart, Yann; Harding, Charlie; Dalgaard, Pia; McKenzie, Christine; Kadirvelraj, Renuka; McKee, Vickie and Nelson, Jane (2002). Cascade chemistry in azacryptand cages: bridging carbonates and methylcarbonates. Dalton Transactions, 8 pp. 1704–1713.



The different tendencies of dinuclear azacryptates of the m-CH2C6H4CH2 and 2,5-furano-spaced hosts L1 and L2 to catalyse CO2 uptake-reactions within these sterically-protected host cavities are examined. Bridging methylcarbonates are generated catalytically upon exposure of methanol solutions of L1, but not L2, di-transition
cation cryptates to atmospheric CO2. X-Ray crystallographic structures of homodinuclear µ-carbonato cryptates of both ligands and µ-methylcarbonato cryptates of L1 with later first transition series cations are reported.
ESI-MS spectra show loss of H2CO3 from µ-carbonato cryptates in collision activation experiments.

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