NOVEL METAL COMPLEXES INVOLVING A MULTIPLY BRIDGED NITROGEN ATOM

A reaction of (t-C4H9N)2S with (π-C5H5)2Ni or [π-C5H5Ni(CO)]2 produced a black, paramagnetic (1.68 BM, g = 2.035), tri-nuclear complex, t-C4H9N(π-C5H5)2Ni)3 (I). The chemical and physical properties of I suggested a trigonal-pyramidal structure with an apical nitrogen atom on a triangle of nickel atoms. The preliminary results of a three-dimensional, singlecrystal X-ray analysis confirmed this structure and revealed a considerable distortion from C3v symmetry. The three Ni-Ni distances are 2.34, 2.27, and 2.21 Å. A similar reaction of (t-C4H9N)2S with π-C5H5Co(CO)2 gave a dark green, binuclear diamagnetic complex, (π-C5H5Co)2(t-C4H9N2)CO (II). Based on the physical measurements, the structure of II was deduced to be a di-t-butylurea complex where each nitrogen atom bridges the two cobalt atoms. The crystal structure has also been determined from single-crystal X-ray analysis which revealed a short Co-Co distance (2.367 Å). A reaction scheme involving a metal-nitrene intermediate was proposed for the formation of II. © 1968, American Chemical Society. All rights reserved.