X-ray structures of dinuclear copper(I) and polynuclear copper(II) complexes with the 2,4-bis(cyanamido)cyclobutane-1,3-dione dianion

From the 2,4-bis(cyanamido)cyclobutane-1,3-dione dianion (2,4-NCNsq2−), two copper complexes [Cu2(PPh3)4(PhCN)2(μ-2,4-NCNsq)] · PhCN (1) and [Cu(dien)(μ-2,4-NCNsq) · H2O]n (2) have been synthesized and characterized by IR and electronic absorption spectroscopies. Their structures have been determined by X-ray crystallography. Complex 1 is a dinuclear copper(I) compound with a 2,4-NCNsq2− ligand bridging two copper atoms through the nitrile nitrogen atoms. Complex 2 appears as a 3D network constituted of copper(II) atoms bridged by 2,4-NCNsq2− dianions. This complex presents an unexpected coordination mode of the bis(cyanamido) ligands which are both coordinated via the nitrile functions and via the amido nitrogen atoms of the NCN groups.

Graphical abstractReactions of copper with 2,4-NCNsq2− yield new complexes presenting a bridging coordination mode. In the copper(I) complex, a bidentate end-on coordination occurs by the two nitrile nitrogen atoms of the NCN groups. For the first time, a tridentate coordination of the 2,4-NCNsq2− ligand is observed in the copper(II) complex.Figure optionsDownload full-size imageDownload as PowerPoint slide