title: A Series of Cyanide-Bridged Binuclear Complexes.
abstract: 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, Et4N{('S3')Ni-CN-Cu[Tp(tBu)]}, 2-Cu.An alternative synthesis was devised for the preparation of the linkages 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. 5 kcal/mol more stable than its linkage isomer.
authors.affiliation: Department of Chemistry and Biochemistry University of Delaware, Newark, Delaware 19716.
authors.forename: Michael T
authors.initials: MT
authors.lastname: Mock
authors.forename: Matthew T
authors.initials: MT
authors.lastname: Kieber-Emmons
authors.forename: Codrina V
authors.initials: CV
authors.lastname: Popescu
authors.forename: Patrick
authors.initials: P
authors.lastname: Gasda
authors.forename: Glenn P A
authors.initials: GP
authors.lastname: Yap
authors.forename: Charles G
authors.initials: CG
authors.lastname: Riordan