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Synthesis and Molecular Structure of (C5Me5)2U(OtBu)(SePh): A Mixed-Ligand Alkoxide-Selenide Uranium(IV) Metallocene Complex Resulting from tert-Butoxy-Trimethylsilane Elimination

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Abstract

The title compound (C5Me5)2U(OtBu)(SePh) (1) was synthesized and characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. This system represents a unique example of an actinide complex with two different group 16 elements coordinated to the metal center and the first mixed-ligand actinide alkoxide-selenide complex. The complex crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 17.830(7) Å, b = 14.973(6) Å, c = 21.254(8) Å, V = 5674(4) Å3, Z = 8, D calc = 1.727 Mg/m3. The uranium(IV) mixed-ligand alkoxide-selenide complex adopts a pseudo-tetrahedral geometry, with the tert-butoxide and phenylselenide ligands occupying the plane bisecting the metallocene unit. Structural comparisons of the complex (C5Me5)2U(OtBu)(SePh) (1) are made with related selenide and alkoxide uranium(IV) complexes.

Graphical Abstract

Reaction of (C5Me5)2U(OtBu)2 with Me3Si-SePh affords the unusual alkoxide-selenide uranium(IV) complex (C5Me5)2U(OtBu)(SePh), which has been characterized by a combination of NMR spectroscopy, elemental analysis, and X-ray crystallography.

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Acknowledgments

For financial support of this work, we acknowledge the Division of Chemical Sciences, Office of Basic Energy Science, Heavy Element Chemistry program, the LANL G.T. Seaborg Institute for Transactinium Science (postdoctoral fellowships to R.K.T. and C.R.G.) and the Los Alamos National Laboratory LDRD program.

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  1. Los Alamos National Laboratory, Mail Stop J514, Los Alamos, NM, 87545, USA

    Robert K. Thomson, Christopher R. Graves, Brian L. Scott & Jaqueline L. Kiplinger

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  1. Robert K. Thomson
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  2. Christopher R. Graves
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  4. Jaqueline L. Kiplinger
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Correspondence to Jaqueline L. Kiplinger.

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Thomson, R.K., Graves, C.R., Scott, B.L. et al. Synthesis and Molecular Structure of (C5Me5)2U(OtBu)(SePh): A Mixed-Ligand Alkoxide-Selenide Uranium(IV) Metallocene Complex Resulting from tert-Butoxy-Trimethylsilane Elimination. J Chem Crystallogr 41, 1241–1244 (2011). https://doi.org/10.1007/s10870-011-0093-8

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