Darstellung und Eigenschaften von trans-Di(fluoro)phthalocyaninato(2–)-rhenat(III); Kristallstruktur des linear-Bis(triphenylphosphin)iminium-Doppelsalzes l(PNP)trans[Re(F)2pc2–] · 0,33l(PNP)F · 2 H2O |
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Authors: | Melanie Gö ldner,Heiner Hü ckstä dt,Heiner Homborg |
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Abstract: | Synthesis and Properties of trans -Di(fluoro)phthalocyaninatorhenate(III); Crystal Structure of the linear -Bis(triphenylphosphine)iminium Double Salt l (PNP) trans[Re(F)2pc2–] · 0.33l (PNP)F · 2 H2O trans-Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II) reacts with (nBu4N)F · 3 H2O in acetone on air yielding trans-di(fluoro)phthalocyaninato(2–)rhenate(III), trans[Re(F)2pc2–]–. The complex anion is precipitated as tetra(n-butyl)ammonium (nBu4N), or after addition of (PNP)HSO4 as linear-bis(triphenylphosphine)iminium (l(PNP)) salt. The latter crystallizes as a double salt of formula l(PNP)trans[Re(F)2pc2–] · 0.33l(PNP)F · 2 H2O in the cubic space group I23 (no. 197) with the cell parameter a = 21.836(2) Å; V = 10412(2) Å3; Z = 6. The Re atom is located in the centre of the (Niso)4 plane (Niso: isoindole-N atom) and coordinates axially two fluorine atoms in a mutual trans position. The Re–N and Re–F distance is 2.035(6) and 1.798(7) Å, respectively. According to the short Re–F distance the asymmetric Re–F stretching vibration is observed in the MIR spectrum at 746 cm–1. Obviously due to a large spin-orbit coupling, the complex salt with an electronic low-spin d4 ground state of ReIII (S = 1) is diamagnetic. Hence a sharp signal is observed at –126.1 ppm in the 19F NMR spectrum. The UV-VIS-NIR spectrum shows the typical π-π* transitions at 15000 (B), 29500 (Q) and 36900 cm–1 (N) and trip-multiplet transitions at 9500/10500 cm–1 and 13200/14100 cm–1. |
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Keywords: | Phthalocyaninates rhenium compounds fluoride compounds optical spectra vibrational spectra 19F nmr spectra crystal structure |
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