Structure and some properties of (alkoxo)(subphthalocyaninato)boron(III)

A few (alkoxo)(subphthalocyaninato)boron(III) complexes, [BX(subpc)] (X=OMe, OEt, OBu(t), and OPh), were prepared and characterized. The molecular structure of [B(OEt)(subpc)] was determined by an X-ray structure analysis; the boron atom is situated 0.642 Angstrom upward from the triangle plane of three isoindoline nitrogen atoms. The geometry of the boron atom is distorted tetrahedral, and the complex shows a wine-glass shape. The mass spectra showed that a part of the hydrogen atoms of the subphthalocyanine ring are displaced by the halogen atoms of boron trihalide or solvents. The complexes showed strong absorption bands at around 560 (Q band) and 300 nm (B band) in chloroform, respectively. The complexes decomposed in solution under irradiation with visible light. The first oxidative or reductive half-wave potential of [B(OEt)(subpc)] was observed at 1.06 V (vs. SCE) or -1.11 V, respectively.