Pseudo-halide uranyl salicylaldiminate complexes including the isolation of a rare uranyl azide

Abstract

<p>We report the synthesis and spectroscopy of pseudo-halide complexes of uranyl coordinated to salicylaldiminate ligands. The reaction of [(NC₉H₆)N=C(H)C₆H₂^<i>t</i>Bu₂O-κ³(O,N,N′)]UO₂Cl(THF), <b>1</b>, with NaN₃ produces a rare example of an uranyl azide, [(NC₉H₆)N=C(H)C₆H₂^<i>t</i>Bu₂O-κ³(O,N,N′)]UO₂(N₃)(THF), <b>2</b>. A series of isocyanates, [(NC₉H₆)N=C(H)C₆H₂^<i>t</i>Bu₂O-κ³(O,N,N′)]UO₂(NCE)(THF), E = O, <b>3</b>; S, <b>4</b>; Se, <b>5</b>, were synthesized from reaction of <b>1</b> with KNCE. Reaction of <b>1</b> with AgNO₃ and AgOTf (OTf = SO₃CF₃) produces [(NC₉H₆)N=C(H)C₆H₂^<i>t</i>Bu₂O-κ³(O,N,N′)]UO₂(NO₃), <b>6</b> and [(NC₉H₆)N=C(H)C₆H₂^<i>t</i>Bu₂O-κ³(O,N,N′)]UO₂(OTf)(THF), <b>7</b>, respectively. The newly formed complexes, <b>2</b>–<b>7</b>, have been characterized by ¹H, ¹³C, and ¹⁵N NMR (where applicable), as well as IR spectroscopy, and the molecular structure of <b>2</b>, <b>5</b>, <b>6</b><b>,</b> and <b>7</b> have been determined by X-ray crystallography.</p