Crystal structure and molecular stereochemistry of the 1:2 adduct of anionic complex, dicyano-(5,10,15,20-tetramesityleneporphinato)-iron(II) with bis(triphenylphosphine)nitrogen (1+)•I2, CDCl3 solvate {[(CN)2FeII(TMP)][PPN]2}•I2•2CDCl3

Treatment of (meso-tetramesityleneporphinato) iron(III) iodide {(TMP)FeI} with four-fold excess equivalents of bis(triphenyl-phosphine)nitrogen(1+) cyanide {[PPN] [CN]} in chloroform solution resulted in the reduction of (TMP)(FeI)-I-III to (TMP)Fe-II and the formation of low-spin bis-cyanide {[(TMP)Fe(CN2)] [PPN](2)} complex cocrystallized with iodine and solvent molecules. The crystal and molecular structure of the complex was established crystallographically. There are two [(TMP)Fe(CN)(2)](2-) anions in the unit cell (one half per asymmetric unit), four [PPN] cations, four CDCl3 molecules and two disordered I-2 molecules (one half per asymmetric unit). The porphyrin macrocycle has crystallographically required C-i = (1) over bar symmetry and is planar with the Fe atom lying at 1/2,0,0. (C) 1998 Elsevier Science S.A. All rights reserved.