Carbonyl derivatives of phthalocyaninatoiron(II), especially those containing group VI axial donor atoms. Crystal and molecular structure of carbonyl( N, N-dimethylformamide)phthalocyaninatoiron(II) and mössbauer studies of some of the products

Abstract

The carbonyl adduct of phthalocyaninatoiron(II), FePc, with N, N-dimethylformamide (DMF) as axial ligand, FePc(CO)DMF, was prepared by the reaction of iron carbonyls, Fe(CO) 5 or Fe 2(CO) 9, with o-phthaalonitrile in DMF as solvent. Several carbonyl adducts of FePc of general formula FePc (CO)L are reported, with L being a ligand with oxygen, sulphur and nitrogen donor atoms (L = tetrahydrofuran, H 2O, CH 3OH, dimethylsulphoxide, tetrahydrothiophene, ammonia, n-propylamine, diethylamine, triethylamine). The crystal and molecular structure of FePc(CO)DMF·DMF was investigaed by X-ray diffraction methods. The compound has a monoclinic unit cell and space group P2 1/ n, a 9.86(1), b 17.35(3), c 19.79(4) », β 87.9(2)°, Z = 4, U 3383 » 3, D 3 1.458 g cm −3. The iron atom is hexacoordinated to the four inner nitrogen atoms of the macrocyle, to carbon monoxide (Fe—C distance 1.72(2) ») and to DMF (Fe—O distance 2.07(1) »). The extra DMF occupies lattice sites. All of the compounds reported in this paper are substantially diamagnetic. Mössbauer spectra show typical isomer shift parameters for the bis-adducts and for the carbonyl adduct, substantially independent of the nature of the axial ligand. The quadrupole splitting parameter of the carbonyl adducts is strongly affected by the nature of the axial ligand.