| Autor: |
Sarkar D; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Vasko P; Department of Chemistry, University of Helsinki, A.I. Virtasen Aukio 1, P.O. Box 55, Helsinki FI-00014, Finland., Roper AF; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Crumpton AE; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Roy MMD; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Griffin LP; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Bogle C; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Aldridge S; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K. |
| Abstrakt: |
The large steric profile of the N-heterocyclic boryloxy ligand, -OB(NDippCH) 2 , and its ability to stabilize the metal-centered HOMO, are exploited in the synthesis of the first example of a "naked" acyclic aluminyl complex, [K(2.2.2-crypt)][Al{OB(NDippCH) 2 } 2 ]. This system, which is formed by substitution at Al I (rather than reduction of Al III ), represents the first O-ligated aluminyl compound and is shown to be capable of hitherto unprecedented reversible single-site [4 + 1] cycloaddition of benzene. This chemistry and the unusual regioselectivity of the related cycloaddition of anthracene are shown to be highly dependent on the availability (or otherwise) of the K + countercation. |
