Some cyclic tetramine complexes of nickel (III) and rhodium (III)

Abstract

In part I of this work, the synthesis of some trivalent nickel complexes with two isomeric hexamethyl-1,4,8,11-tetra-azacyclotetradecanes (tet a = 5,7,7,12,14,14-hexamethyl.... (C meso); and tet c = 5,7,7,12,12,14-hexamethyl.... (C racemic)), and nitrato or sulphato ligands are described. Infrared spectra indicate that the nitrato groups are monodentate, and that the sulphato groups are probably bridging. Electronic spectra are reported. Magnetic moments in the range 1.8-2.2 B.M. are reported for the nitrato complexes. The sulphato complexes show anomalous magnetic behaviour, consistent with antiferromagnetism. A structure which would allow magnetic exchange is postulated for these compounds. In part II, the synthesis of trivalent rhodium complexes of two isomeric 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetra-decanes (tet a = C meso, and tet b = C racemic) are described. Trans derivatives [Rh tet a XY]+, X = Y = Cl-, Br, I-, CH3COO-; X = Cl-, Y = NCS-; and [Rh tet b XY]+, X = Y = Cl-, Br-, I-, NCS-, and possibly CI04-; X = Cl-, Y = NCS-, are described. The cis derivatives [Rh tet b A]+, where A = C03 = or C204=; and [Rh tet b Cl]2Cl4 (dimeric), are described. The infrared and electronic spectra are reported.