Darstellung und Eigenschaften von Diphthalocyaninaten des Bismuts, [Bi(Pc)2]k (k = 1−, 0, 1+); Kristallstruktur von gemischtvalentem [Bi(Pc)2] · CH2Cl2 |
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| Authors: | G. Ostendorp H. Homborg |
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| Abstract: | ![]()
Synthesis and Properties of Diphthalocyaninates of Bismuth, [Bi(Pc)2]k (k = 1?, 0, 1+); Crystal Structure of mixed-valent [Bi(Pc)2] · CH2Cl2 Blue di(phthalocyaninato(2-))bismuthate(III), [Bi(Pc2?)2]?, is obtained by the reaction of BiO(NO3) with molten 1,2-dicyanobenzene in the presence of potassium methylate and isolated as tetra-n-butylammonium (nBu4N)+ and bis(triphenylphosphine)iminium (PNP)+ salt. Green mixed-valent [Bi(Pc)2] · CH2Cl2 is prepared by anodic oxidation of [Bi(Pc2?)2]?. It crystallizes in the orthorhombic γ modification (Pnma; a = 28.176(5), b = 22.913(3), c = 7.925(1) Å, Z = 4). The BiIII ion is eightfold coordinated by the Niso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi? Niso bond distance is 2.467 Å. The complex is paramagnetic (μeff = 1.84 μB). Oxidation of [Bi(Pc2?)2]? with bromine yields purple, diamagnetic [Bi(Pc?)2]Brx (1.5 ≤ x ≤ 2.5). The redox properties are investigated electrochemically. UV-Vis-NIR, MIR/FIR and resonance Raman spectra of the new bismuth(III) complexes are discussed and compared with those of diphthalocyaninates of the lanthanides. |
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| Keywords: | Diphthalocyaninates bismuth(III) compounds crystal structure electrochemistry optical spectra vibrational spectra |
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