A series of cyanide-bridged binuclear complexes, (‘S 3 ’)Ni–CN–M[Tp tBu ] (‘S 3 ’=bis(2-mercaptophenyl)sulfide, Tp tBu =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[(‘S 3 ’)Ni(CN)] with [Tp tBu ]MX. The isostructural series of complexes was structurally and spectroscopically characterized. A similar coupling strategy was used to synthesize the anionic copper(I) analogue, Et 4 N{(‘S 3 ’)Ni–CN–Cu[Tp tBu ]}, 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, 13 C 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. 5kcal/mol more stable than its linkage isomer.