3 years ago

Synthesis and Characterization of [Rb([18]crown-6)]3As15Zn·4NH3 and [Rb([2.2.2]crypt)]4Sb14Zn·8NH3

Synthesis and Characterization of [Rb([18]crown-6)]3As15Zn·4NH3 and [Rb([2.2.2]crypt)]4Sb14Zn·8NH3
Marina Kaas, Nikolaus Korber
The new compound [Rb([18]crown-6)]3As15Zn·4NH3 was obtained by the reaction of Rb3As7, ZnPh2, [18]crown-6, and [2.2.2]crypt in liquid ammonia. The black monoclinic crystals contain the (As15Zn)3– anion, in which two As73– cages are linked by an As–Zn unit. The anionic units are separated by cationic [Rb([18]crown-6)]+ units. The analogous reaction of Rb3Sb7, ZnPh2, [18]crown-6, and [2.2.2]crypt yielded black triclinic crystals of the compound [Rb([2.2.2]crypt)]4Sb14Zn·8NH3. This is the first antimony derivative with the (E14Zn)4– anionic motif, which consists of two nortricyclane like cages linked by a Zn atom. Quantum chemical calculations on the anionic units confirm that the electron density is mainly found at the periphery of the cluster system. This phenomenon is in accord with the observations already reported for the 1,2,3-tripnicolides.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/zaac.201700171

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