Sodium complexes containing 2-iminopyrrolyl ligands: the influence of steric hindrance in the formation of coordination polymers.

Iminopyrrolyl complexes of sodium were prepared from the reaction of 2-arylformiminopyrrole ligand precursors (aryl = C(6)H(5) (I); 2,6-Me(2)C(6)H(3) (II); 2,4,6-Me(3)C(6)H(2) (III); 2,6-(i)Pr(2)C(6)H(3) (IV)) with one equivalent of sodium hydride. The resulting corresponding compounds 1-4, [{Na(mu(2):kappa(2)N,N'-iminopyrrolyl)}(2n)(OEt(2))(2x)] (n > or = 1; x = 0 or 1), were obtained in moderate to high yields and were characterised by NMR spectroscopy, high resolution mass spectrometry and X-ray diffraction, when suitable crystals were obtained. The X-ray structure of compound 1 (n >> 1; x = 0) reveals the formation of a coordination polymer with repeating units consisting of dimers that contain two iminopyrrolyl ligands chelating two sodium atoms, where both pyrrolyl rings exhibit bridging sigma + sigma coordination to the Na atoms within the dimer; the self-assembling of the polymer is established by additional pi-bonds (eta(5)-coordination) of each of the pyrrolyl rings to the sodium atoms of the adjacent dimer units. Conversely, the structure of complex D(IV) (n = x = 1) shows it as one of such dimers capped by two diethyl ether molecules, each coordinated to the sodium atoms (n = 2; x = 1). DFT calculations indicate that the differences between the structures 1-4 of arise from the increasing bulkiness imposed by the corresponding substituents of the iminic aryl groups.