This post is about what I spent the first year of my DPhil doing. Between Bryan Eichhorn's work with group 6 and group 10 transition metal compounds and the work I did for my Part II project with Cu, Zn, Cd and In compounds, the reactivity of group 15 Zintl ions towards organometallic reagents has been well studied. However, interestingly, there didn't seem to be any research on the reactivity of E73– towards simple metal halide salts. This seemed strange for a couple of reasons. Firstly, practically every metal has at least one comercially available halide, whereas many organometallic compounds cannot be purchased and have to be synthesised in the lab. Secondly, the syntheses of many organometallics start from the metal halide, therefore surely it would be logical to try reacting E73– with the metal halide first, before going to the trouble of synthesising the organometallic compound? I therefore started my DPhil looking at the reactivity of group 15 Zintl ions towards metal halide salts, namely the group 13 chlorides InCl3 and TlCl.
Both K3P7 and K3As7
react with InCl3 in ethylenediamine and in the presence of 2,2,2-crypt to form [K(2,2,2-crypt)]3[In(E7)2] (E = P, As). These compounds contain the In-bridged cluster anions [In(P7)2]3– and
[In(As7)2]3–. The crystal structure of [In(P7)2]3–
shows two P73– cages bridged by an In atom. Each P73– is bonded to the In in an η2-fashion, resulting in a distorted tetrahedral coordination geometry. [In(P7)2]3–
is isoelectronic with the [Zn(P7)2]4–
and [Cd(P7)2]4– species I discussed in my previous post.
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[In(P7)2]3–.
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K3P7 and K3As7
also react with TlCl in ethylenediamine and in the presence of 2,2,2-crypt or 18-crown-6 to form [K(2,2,2-crypt)]2[TlP7] and
[K(18-crown-6)]2[TlAs7], which contain the Tl-functionalised cluster anions [TlP7]2– and [TlAs7]2–. The crystal structures of both species show an E73– cluster bonded to a Tl atom in an η2-fashion.
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[TlP7]2– and [TlAs7]2–.
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So that's another small taster of the research I've been doing. Why not read the paper if you want to know more? I will hopefully be writing about more of my own research in the future, depending on how the experiments I'm doing at the moment pan out. Watch this space!
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