BIS(BIS(TRIPHENYLPHOSPHINE)IMINIUM) MU-NI TRIDO-BIS(AZIDOPHTHALOCYANINATO(2-)FERRATE(IV)) TRIIODIDE DIETHYLETHER DI-SOLVATE - SYNTHESIS, PROPERTIES, AND CRYSTAL-STRUCTURE

Bis(bis(triphenylphosphine)iminium) nitrido-bis(azidophthalocyaninato) (2-)ferrate(IV)) triiodide is prepared as a diethylether di-solvate by substitution of u-nitrido-bis(pyridinephthalocyaninato(2-)iron(Iv) pe ntaiodide with bis(triphenylphosphine)iminium azide in acetone and pre cipitation by slow diffusion of diethylether. The doublesalt crystalli zes monoclinically in the space group C12/c1 with cell parameters: a = 34.567(9) Angstrom, b = 20.237(9) Angstrom, c = 21.251(5) Angstrom, b eta = 119.79(2)degrees; Z = 4. The Fe atoms are located almost in the centre (Ct) of the (N-iso)(4) planes (d(Fe-Ct) = 0.080(1) Angstrom; N- iso: isoindole N atom). The average Fe-N-iso distance is 1.947(5) Angs trom, the Fe-(mu-N) distance 1.650(1) Angstrom. The Fe-(mu-N)-Fe skele ton is linear (177.4(4)degrees). Both waving pc(2-) ligands are in a s taggered conformation (skew angle phi = 38.5(5)degrees). Fe coordinate s Linear azide (d(Fe-N-azide) = 2.152(7) Angstrom) with an angle of 12 1.2(6)degrees. The isolated triiodide ion is almost linear (d(I-I) = 2 .936(2) Angstrom). The PNP cation obtains an hybrid conformation (angl e(P-N-P) = 157.4(2)degrees). The asymmetrical Fe-(mu-N)-Fe stretching vibration is observed in the IR spectrum at 997 cm(-1), the symmetrica l one is selectively enhanced in the resonance Raman (RR) spectrum at 478 cm(-1). The corresponding I-I stretching vibrations of the triiodi de ion are present in the actual spectra at 134 (IR) and 115 cm(-1) (R R). An IR band at 334 cm(-1) is attributed to the asymmetrical Fe-N-az ide stretching vibration.