A series of cyanide-bridged binuclear complexes

A series of cyanide-bridged binuclear complexes, (‘S3’)Ni–CN–M[TptBu] (‘S3’ = bis(2-mercaptophenyl)sulfide, TptBu = hydrotris(3-tert-butylpyrazolyl)borate, M = Fe (2-Fe), Co (2-Co), Ni (2-Ni), Zn (2-Zn)) was prepared by the coupling of K[(‘S3’)Ni(CN)] with [TptBu]MX. The isostructural series of complexes was structurally and spectroscopically characterized. A similar coupling strategy was used to synthesize the anionic copper(I) analogue, Et4N{(‘S3’)Ni–CN–Cu[TptBu]}, 2-Cu.An alternative synthesis was devised for the preparation of the linkage isomers of 2-Zn, i.e. of cyanide-bridged linkage isomers. X-ray diffraction, 13C NMR and IR spectral studies established that isomerization to the more stable Ni–CN–Zn isomer occurs. DFT computational results buttressed the experimental observations indicating that the cyanide-bridged isomer is ca. 5 kcal/mol more stable than its linkage isomer.

Graphical abstractA series of binuclear Ni–CN–M (M = Fe, Co, Ni, Cu and Zn) complexes have been prepared and structurally characterized.Figure optionsDownload full-size imageDownload as PowerPoint slide