Synthesis and structure of a terminal uranium nitride complex |
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Authors: | King David M Tuna Floriana McInnes Eric J L McMaster Jonathan Lewis William Blake Alexander J Liddle Stephen T |
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Institution: | School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK. |
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Abstract: | The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex UN(Tren(TIPS))]Na(12-crown-4)(2)] {in which Tren(TIPS) = N(CH(2)CH(2)NSiPr(i)(3))(3)](3-) and Pr(i) = CH(CH(3))(2)} by reaction of the uranium(III) complex U(Tren(TIPS))] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of (15)N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water. |
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