Abstract
The compound cis-FeCl2(DMPI)4 (DMPI = 2,6-dimethylphenyl isocyanide) was synthesized and characterized by X-ray crystallography, IR spectroscopy, and 1H-NMR. The structure of the hexanes solvate was solved in space group C2/c with a = 16.4160(2), b = 15.8028(2), c = 14.1263(2) A, β = 92.345(1), V = 3661.56(8) A3, Z = 4, with R = 0.0385. The coordination geometry about the Fe(II) center was octahedral with the two chlorides cis disposed. This is the first crystal structure of a cis-dihalotetrakis(isocyanide)iron(II) complex, and the isocyanide ligands trans to the chlorides are shown to participate in π-backbonding while those cis to the chlorides do not. IR spectroscopy confirms these observations, and 1H-NMR is consistent with the presence of two different types of isocyanide ligands. The structure and spectroscopy of cis-dichlorotetrakis(2,6-dimethylphenyl isocyanide)iron(II) revealed a complex with two types of isocyanide ligands: those trans to chloride which participate in π-backbonding from iron, and those cis to chloride which do not participate in π-backbonding.
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