Tl(I)-, Cu(I)-, and Ag(I) complexes of the ditopic 1,3-phenylene-bridged heteroscorpionate ligand [1,3-C6H4(tBuBpz2)2]2-

The complexes Tl-2[1,3-C6H4(tBuBpz(2))(2)] (1Tl), [Cu(PPh3)](2)[1,3-C6H4(tBuBpz(2))(2)] (1Cu), and [Ag(PPh3)](2)[1,3-C6H4(tBuBpz(2))(2)] (1Ag) featuring a novel ditopic 1,3-phenylene-bridged heteroscorpionate ligand have been prepared and investigated by H-1, C-13, B-11, and P-31 NMR spectroscopy (pz = pyrazolyl). X-ray crystal structure analyses revealed 1Tl and 1Ag to adopt a trans configuration with respect to the phenylene bridge in the solid state. In solution at room temperature, both scorpionate substituents are free to rotate about their B-C(phenylene) bonds. The Tl(I) coordination to two pyrazolyl nitrogen atoms as well as the Ag(I) coordination to two pyrazolyl and one PPh3 ligand is augmented by short intramolecular contacts to the phenylene pi-system.