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The field of calixarene chemistry has grown substantially in the past decade. There are now many reported applications including sensors, medical diagnostics and phase transfer agents. [1] Use in polymerisation catalysis for a variety of chemical systems has, however, only recently gained attention with mixed success. [2-6] This paper focuses on our discoveries with early transition metal (primarily vanadium) oxo or organoimido fragments supported on the hexahomotrioxacalix[3]arene ligand (see figure for an example) or by one of a range of new tripodal ligands. Oxacalix[3] ligands have gained very little attention in the literature thus far, in contrast to the rich literature for the well-known calix[4]arenes. Here we report the structures and high ethylene polymerisation catalytic activity of the new compounds. The structural work has been undertaken using both laboratorybased conventional X-ray sources and synchrotron radiation at Daresbury Laboratory, all at low temperature.

Early transition metal calixarene and tripod ligand complexes for ethylene polymerisation