Synthesis and structure of the coordinatively unsaturated boron subphthalocyanine cation, [B(SubPc)]+

The boron subphthalocyanine cation, B(SubPc)+, has been prepared as a salt of a weakly coordinating carborane anion, CHB11Me 5Br6-, by a metathesis reaction of Et 3Si(CHB11Me5Br6) with B(SubPc)Cl. The separation of the cation and anion in the X-ray structure indicates coordinative unsaturation at the boron center, and this is corroborated by DFT calculations. A strongly Lewis acidic nature for the B(SubPc)+ cation is indicated by its hydrolysis to an unusual product, the di-meso-N-protonated -oxo dimer, [H(SubPc)B-O-B(SubPc)H]2+. ©2006 Wiley Periodicals, Inc.