Oxime-substituted NCN-pincer palladium and platinum halide polymers through non-covalent hydrogen bonding (NCN = [C6H2(CH2NMe2)2-2,6]−)

The oxime-substituted NCN-pincer molecules HONCH-1-C6H3(CH2NMe2)2-3,5 (2a) and HONCH-4-C6H2(CH2NMe2)2-2,6-Br-1 (2b) were accessible by treatment of the benzaldehydes H(O)C-4-C6H3(CH2NMe2)2-3,5 (1a) and H(O)C-4-C6H2(CH2NMe2)2-2,6-Br-1 (1b) with an excess of hydroxylamine. In the solid state both compounds are forming polymers with intermolecular O–HN connectivities between the Me2NCH2 substituents and the oxime entity of further molecules of 2a and 2b, respectively. Characteristic for 2a and 2b is a helically arrangement involving a crystallographic 21 screw axis of the HONCH-1-C6H3(CH2NMe2)2-3,5 and HONCH-4-C6H2(CH2NMe2)2-2,6-Br-1 building blocks. The reaction of 2b with equimolar amounts of [Pd2(dba)3 · CHCl3] (3) (dba = dibenzylidene acetone) or [Pt(tol)2(SEt2)]2 (4) (tol = 4-tolyl) gave by an oxidative addition of the C–Br unit to M coordination polymers with a [(HONCH-4-C6H2(CH2NMe2)2-2,6)MBr] repeating unit (5: M = Pd, 6: M = Pt). Complexes 5 and 6 are in the solid state linear hydrogen-bridged polymers with O–HBr contacts between the oxime entities and the metal-bonded bromide.