PREPARATION AND PROPERTIES OF TETRA(N-BUTYL)AMMONIUM CIS-TRIFLUOROPHTHALOCYANINATO(2-)ZIRCONATE(IV) AND CIS-TRIFLUOROPHTHALOCYANINATO(2-)HAFNATE(IV) - CRYSTAL-STRUCTURE OF ((BU4N)-BU-N)(CIS)[HF(F)(3)PC(2-)]

cis-Dichlorophthalocyaninato(2-)metal(IV) of zirconium and hafnium rea cts with excess tetra(n-butyl)ammoniumfluoride trihydrate to yield tet ra(n-butyl)ammonium cis-trifluorophthalocyaninato(2-)metalate(IV), ((B u4N)-Bu-n)(cis)[M(F)(3)pc(2-)] (M=Zr, Hf). ((Bu4N)-Bu-n)(cis)[Hf(F)(3) pc(2-)] crystallizes in the monoclinic space group P2(1)/n (#14) with cell parameters a=13.517(1) Angstrom, b=13.856(1) Angstrom, c=23.384(2 ) Angstrom, alpha=92.67(1)degrees, Z=4. The Hf atom is in a ''square b ase-trigonal cap'' polyhedron, coordinating three fluorine atoms and f our isoindole nitrogen atoms (N-iso). The Hf atom is sandwiched betwee n the (N-iso)(4) and F-3 planes (d(Hf-Ct(N))=1.218(3) Angstrom; d(Hf-C t(F))=1.229(3) Angstrom; Ct(N/F): centre of the (N-iso)(4), respective ly F-3 plane). The average Hf-N-iso and Hf-F distances are 2.298 and 1 .964 Angstrom, respectively, the average F-Hf-F angle is 84.9 degrees. The pc(2-) ligand is concavely distorted. The optical spectra show th e typical metal independent pi-pi transitions of the pc(2-) ligand at c. 14700 and 29000 cm(-1). In the FIR/MIR spectra vibrations of the M F3 skeleton are detected at 545, 489, 274 cm(-1) (M = Zr) and 536, 484 , 263 cm(-1) (M = Hf), respectively.