3 research outputs found
Pseudo-halide uranyl salicylaldiminate complexes including the isolation of a rare uranyl azide
No full text<p>We report the synthesis and spectroscopy of pseudo-halide complexes of uranyl coordinated to salicylaldiminate ligands. The reaction of [(NC<sub>9</sub>H<sub>6</sub>)N=C(H)C<sub>6</sub>H<sub>2</sub><sup><i>t</i></sup>Bu<sub>2</sub>O-κ<sup>3</sup>(O,N,N′)]UO<sub>2</sub>Cl(THF), <b>1</b>, with NaN<sub>3</sub> produces a rare example of an uranyl azide, [(NC<sub>9</sub>H<sub>6</sub>)N=C(H)C<sub>6</sub>H<sub>2</sub><sup><i>t</i></sup>Bu<sub>2</sub>O-κ<sup>3</sup>(O,N,N′)]UO<sub>2</sub>(N<sub>3</sub>)(THF), <b>2</b>. A series of isocyanates, [(NC<sub>9</sub>H<sub>6</sub>)N=C(H)C<sub>6</sub>H<sub>2</sub><sup><i>t</i></sup>Bu<sub>2</sub>O-κ<sup>3</sup>(O,N,N′)]UO<sub>2</sub>(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 AgNO<sub>3</sub> and AgOTf (OTf = SO<sub>3</sub>CF<sub>3</sub>) produces [(NC<sub>9</sub>H<sub>6</sub>)N=C(H)C<sub>6</sub>H<sub>2</sub><sup><i>t</i></sup>Bu<sub>2</sub>O-κ<sup>3</sup>(O,N,N′)]UO<sub>2</sub>(NO<sub>3</sub>), <b>6</b> and [(NC<sub>9</sub>H<sub>6</sub>)N=C(H)C<sub>6</sub>H<sub>2</sub><sup><i>t</i></sup>Bu<sub>2</sub>O-κ<sup>3</sup>(O,N,N′)]UO<sub>2</sub>(OTf)(THF), <b>7</b>, respectively. The newly formed complexes, <b>2</b>–<b>7</b>, have been characterized by <sup>1</sup>H, <sup>13</sup>C, and <sup>15</sup>N 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
High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes
No full textPtÂ(IV)
complexes <i>trans</i>-PtÂ(PEt<sub>3</sub>)<sub>2</sub>(R)Â(Br)<sub>3</sub> (R = Br, aryl and polycyclic aromatic fragments) photoeliminate
molecular bromine with quantum yields as high as 82%. Photoelimination
occurs both in the solid state and in solution. Calorimetry measurements
and DFT calculations (PMe<sub>3</sub> analogs) indicate endothermic
and endergonic photoeliminations with free energies from 2 to 22 kcal/mol
of Br<sub>2</sub>. Solution trapping experiments with high concentrations
of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor
to bromine elimination
High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes
No full textPtÂ(IV)
complexes <i>trans</i>-PtÂ(PEt<sub>3</sub>)<sub>2</sub>(R)Â(Br)<sub>3</sub> (R = Br, aryl and polycyclic aromatic fragments) photoeliminate
molecular bromine with quantum yields as high as 82%. Photoelimination
occurs both in the solid state and in solution. Calorimetry measurements
and DFT calculations (PMe<sub>3</sub> analogs) indicate endothermic
and endergonic photoeliminations with free energies from 2 to 22 kcal/mol
of Br<sub>2</sub>. Solution trapping experiments with high concentrations
of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor
to bromine elimination
