The field of transition-metal cyanide chemistry has undergone a renaissance over the past two decades due to the role that cyanide plays in providing building blocks for molecular magnetic materials. Of particular interest are the 4d and 5d metals which benefit from increased spin-orbit coupling, a wider range of oxidation states, and more diffuse valence orbitals as compared to the 3d metals. In terms of homoleptic cyanometallates, those of the second and third row metals are much less studied than their 3d congeners, a situation that we would like to remedy. Our recent efforts to obtain new building blocks of cyanotungstate species, beyond the well known [WV(CN)8]3- and [WIV(CN)8]4- anions, have recently been successful. We have synthesized and crystallographically characterized the first [W(CN)7]4- species from reduction of (n-Bu4N)3[W(CN)8]. Characterization includes infrared spectroscopy, SQUID magnetometry, and electrochemistry to understand its structure and reactivity. The synthesis, structural studies, and further experiments will be presented and discussed.

Synthesis and characterization of new heavy element cyanide compounds

248th National Meeting (2014)

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