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Neptunocene

Neptunocene, Np(C<sub>8</sub>H<sub>8</sub>)<sub>2</sub>, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT<sup>2-</sup>) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in which it is sparingly soluble. The compound is quite air-sensitive.

It was one of the first organoneptunium compounds to be synthesised, and is a member of the actinocene family of actinide-based metallocenes.

Structure

The sandwich structure of neptunocene has been determined by single crystal XRD. The COT<sup>2-</sup> rings are found to be planar with 8 equivalent C–C bonds of 1.385 Å length, and sit parallel in an eclipsed conformation. The Np–COT distance (to the ring centroid) is 1.909 Å and the individual Np–C distances are 2.630 Å.

Neptunocene assumes a monoclinic crystal structure (P2<sub>1</sub>/n space group) which is isomorphous to uranocene and thorocene but not to plutonocene.

Synthesis and properties

Neptunocene was first synthesised in 1970 by reacting neptunium(IV) chloride (NpCl<sub>4</sub>) with dipotassium cyclooctatetraenide (K<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>)) in diethyl ether or THF:

NpCl<sub>4</sub> + 2 K<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>) → Np(C<sub>8</sub>H<sub>8</sub>)<sub>2</sub> + 4 KCl

The same reaction conditions have been routinely reproduced since then for the synthesis of the compound.

The three actinocenes uranocene, neptunocene, and plutonocene share virtually identical chemistry: they do not react in the presence of water or dilute base, but are very air-sensitive, quickly forming oxides. All three are only slightly soluble (up to about 10<sup>−3</sup> M concentrations) in aromatic or chlorinated solvents such as benzene, toluene, carbon tetrachloride or chloroform.

References