Add time:08/16/2019         Source:sciencedirect.com

The results of an investigation of the bonding mode of the cyanate ion in complexes of copper(II) and nickel(II) containing 4-substituted pyridine derivatives and various other aromatic π-acceptor amines indicate that the bonding mode of the cyanate is rather insensitive to the electronic environment in these complexes and continues to bond through the nitrogen atom. Infrared and VIS-UV spectral data indicate that the [CuL2(NCO)2] complexes generally involve square planar geometry with trans monodentate ligands (cis, of course, with bidentate ligands) and the [NiL4(NCo)2] complexes are trans octahedral (except for cis-[Ni(1,10-phenanthroline)2(NCO)2]). Significant exceptions to these generalizations include [Cu(4-pyridinealdoxime)2(NCO)2], which is believed to exhibit octahedral geometry due to bridging aldoxime groups; [Cu(quinoline)2(NCO)2] and [Cu(6-nitroquinoline)2], which are probably distorted tetrahedral complexes due to steric interactions encountered by the hydrogen atoms at the 8-positions of the quinoline molecules; and [Cu(quinoline)(NCO)2], [Ni(4-cyanopyridine)2(NCO)2] and [Ni(4-carbomethoxypyridine)2(NCO)2], which are postulated as being the first examples, along with K[Cd(NCO)3] of complexes involving bridging cyanate groups The latter complex appears to have a dimeric structure with four terminal N-bonded cyanates and two bridging cyanates, analogous to the structure suggested in the literature for [n-C4H9)4N]2[Cd2(NCSe)6].

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