A series of cyanide-bridged binuclear complexes |
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Authors: | Michael T Mock Codrina V Popescu Glenn PA Yap |
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Institution: | a Department of Chemistry and Biochemistry, University of Delaware, Brown Laboratory, Newark, Delaware 19716, United States b Department of Chemistry, Ursinus College, Collegeville, Pennsylvania 19426, United States |
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Abstract: | A series of cyanide-bridged binuclear complexes, (‘S3’)Ni-CN-MTptBu] (‘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-CuTptBu]}, 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. |
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Keywords: | Cyanide Cyanide-bridged Binuclear complex Linkage isomers Tp |
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