Actinide Hydride Complexes as Multielectron Reductants: \nAnalogous Reduction Chemistry from [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH]<sub>2</sub>,\n[(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH<sub>2</sub>]<sub>2</sub>, and [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>ThH<sub>2</sub>]<sub>2</sub>
William J. Evans (529233)Kevin A. Miller (2102332)Stosh A. Kozimor (1615057)Joseph W. Ziller (1340067)Antonio G. DiPasquale (1274730)Arnold L. Rheingold (1274736)
Abstract
Methods to separate the components of the equilibrium mixture of [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH]<sub>2</sub> and [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH<sub>2</sub>]<sub>2</sub> have been developed that allow their reductive chemistry to be studied. These actinide hydrides\ncan act as four-, six-, and eight-electron reductants depending on the substrate with H<sub>2</sub> as the byproduct\nof a H<sup>-</sup> → e<sup>-</sup> + <sup>1</sup>/<sub>2</sub> H<sub>2</sub> redox couple. This hydride reduction chemistry allows complexes of redox-inactive Th<sup>4+</sup> such as [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>ThH<sub>2</sub>]<sub>2</sub> to be four- and six-electron reductants. [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH]<sub>2</sub> and [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH<sub>2</sub>]<sub>2</sub> cleanly reduce 2 equiv of PhEEPh (E = S, Se) to form 2 equiv of (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>U(SPh)<sub>2</sub> and\n(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>U(SePh)<sub>2</sub> in an overall four-electron reduction in each case. [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH]<sub>2</sub> and [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH<sub>2</sub>]<sub>2</sub> also effect a six-electron reduction of 3 equiv of 1,3,5,7-cyclooctatetraene to [(C<sub>5</sub>Me<sub>5</sub>)(C<sub>8</sub>H<sub>8</sub>)U]<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>) and an eight-electron reduction of 2 equiv of PhNNPh to form 2 equiv of the U<sup>6+</sup> imido complex\n(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>U(NPh)<sub>2</sub>. In each reaction, H<sub>2</sub> is a byproduct. This hydride-based reduction is also successful\nwith the tetravalent thorium hydride [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>ThH<sub>2</sub>]<sub>2</sub>, which reduces 2 equiv of PhSSPh to (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Th(SPh)<sub>2</sub> and 3 equiv of C<sub>8</sub>H<sub>8</sub> to [(C<sub>5</sub>Me<sub>5</sub>)(C<sub>8</sub>H<sub>8</sub>)Th]<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>) with concomitant formation of H<sub>2</sub>. X-ray\ncrystallographic data are reported on [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH]<sub>2</sub>, [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>UH<sub>2</sub>]<sub>2</sub>, and (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>U(SePh)<sub>2</sub> as well as\nthe thorium reduction products (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Th(SPh)<sub>2</sub> and [(C<sub>5</sub>Me<sub>5</sub>)(C<sub>8</sub>H<sub>8</sub>)Th]<sub>2</sub>(C<sub>8</sub>H<sub>8</sub>).
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