SYNTHESIS AND PROPERTIES OF TRANS-DI(FLUO RO)PHTHALOCYANINATO(2-)RHENATE(III) - CRYSTAL-STRUCTURE OF THE LINEAR-BIS(TRIPHENYLPHOSPHINE)IMINIUM DOUBLE SALT )(PNP)(TRANS)[RE(F)(2)PC(2-)].0.33(L)(PNP)F.2H(2)O

trans-Bis(triphenylphosphine)phthalocyanato (2-)rhenium(II) reacts wit h ((Bu4N)-Bu-n)F . 3H(2)O in acetone on air yielding trans-di(fluoro)p hthalocyaninato(2-)rhenate(III), (trans)[Re(F)(2)pc(2-)](-). The compl ex anion is precipitated as tetra(n-butyl)ammonium ((Bu4N)-Bu-n), or a fter 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)(2)pc(2-)]. 0.33(l)(PNP)F . 2H(2)O in the cubic spac e group I23 (no.197) with the cell parameter a = 21.836(2) Angstrom; V = 10412(2) Angstrom(3); Z = 6. The Re atom is located in the centre o f the (N-iso)(4) plane (N-iso: isoindole-N atom) and coordinates axial ly two fluorine atoms in a mutual trans position. The Re-N and Re-F di stance is 2.035(6) and 1.798(7) Angstrom, respectively. According to t he short Re-F distance the asymmetric Re-F stretching vibration is obs erved in the MIR spectrum at 746 cm(-1). Obviously due to a large spin -orbit coupling, the complex salt with an electronic low-spin d(4) gro und state of Re-III (S = 1) is diamagnetic. Hence a sharp signal is ob served at -126.1 ppm in the (FNMR)-F-19 spectrum. The UV-VIS-NIR spect rum shows the typical pi-pi transitions at 15000 (B), 29500 (Q) and 3 6900 cm(-1) (N) and trip-multiplet transitions at 9500/10500 cm(-1) an d 13200/14100 cm(-1).