Boron-scorpionates are readily prepared by microwave (MW) assisted methods. Such a method is described here, leading to the rapid preparation of a heterogeneous resin-supported scorpionate as its sodium salt, BdPhTpNa [BdPhTp = phenyltris(1-pyrazolyl)borate covalently bound through the phenyl ring to commercial cross-linked polystyrene resin beads]. Formation of a functional heterogeneous scorpionate was confirmed from the subsequent reactions of several metal complexes. This supported ligand system coordinates a variety of transition metal ions including copper(I and II), chromium(III) and rhodium(I). Chromium(III) provided definitive electronic [a] 2465 spectral evidence for supported-TpCr III coordination spheres, including reversible ligand-substitution reactions. The copper(I) case exhibited typical scorpionate Cu I reactivity including spectroscopically characterized (IR and 31 P NMR) complexes with CO, PPh 3 , and HCCH. Copper(II) provided EPR evidence for heterogeneous scorpionates. The supported rhodium(I) complex was demonstrated to be a recyclable heterogeneous rhodium-scorpionate catalyst. These results all support the conclusion that the immobilized chelate forms coordinatively unsaturated halfsandwich metal complexes (LM n+ ) capable of efficient ligandsubstitution reactions or catalytic activity.
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