Synthesis, Characterization, and Stoichiometric U–O Bond Scission in Uranyl Species Supported by Pyridine(diimine) Ligand Radicals

Synthesis, Characterization, and Stoichiometric U–O Bond Scission in Uranyl Species Supported by Pyridine(diimine) Ligand Radicals

Two uranium­(VI) uranyl compounds, Cp*UO2­(MesPDIMe) (3) and Cp*UO2( t Bu-MesPDIMe) (3- t Bu) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienide; MesPDIMe = 2,6-((Mes)­N=CMe)2C5H3N; t Bu-MesPDIMe = 2,6-((Mes)­N=CMe)2-p-C­(CH3)3C5H2N; Mes = 2,4,6-trimethylphenyl), have been synthesized by addition of N-me...

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Veröffentlicht in:Journal of the American Chemical Society 2015-09, Vol.137 (34), p.11115-11125
Hauptverfasser: Kiernicki, John J, Cladis, Dennis P, Fanwick, Phillip E, Zeller, Matthias, Bart, Suzanne C
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container_issue 34
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creator Kiernicki, John J
Cladis, Dennis P
Fanwick, Phillip E
Zeller, Matthias
Bart, Suzanne C
description Two uranium­(VI) uranyl compounds, Cp*UO2­(MesPDIMe) (3) and Cp*UO2( t Bu-MesPDIMe) (3- t Bu) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienide; MesPDIMe = 2,6-((Mes)­N=CMe)2C5H3N; t Bu-MesPDIMe = 2,6-((Mes)­N=CMe)2-p-C­(CH3)3C5H2N; Mes = 2,4,6-trimethylphenyl), have been synthesized by addition of N-methylmorpholine N-oxide to trianionic pyridine­(diimine) uranium­(IV) precursors, Cp*U­(MesPDIMe)­(THF) (1), Cp*U­(MesPDIMe)­(HMPA) (1-HMPA), and Cp*U­( t Bu-MesPDIMe)­(THF) (1- t Bu). These uranyl complexes contain singly reduced pyridine­(diimine) ligands suggesting formation occurs via cooperative ligand/metal oxidation. Treating 3 or 3- t Bu with stoichiometric equivalents of Me3SiI results in stepwise oxo silylation to form (Me3SiO)2UI2(MesPDIMe) (5) or (Me3SiO)­UI2( t Bu-MesPDIMe) (5- t Bu), respectively. Additional equivalents result in full uranium–oxo bond scission and formation of UI4(1,4-dioxane)2 with extrusion of hexamethyldisiloxane. The uranium complexes have been characterized via multinuclear NMR, vibrational, and electronic absorption spectroscopies and, in some cases, X-ray crystallography.
doi_str_mv 10.1021/jacs.5b06217
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These uranyl complexes contain singly reduced pyridine­(diimine) ligands suggesting formation occurs via cooperative ligand/metal oxidation. Treating 3 or 3- t Bu with stoichiometric equivalents of Me3SiI results in stepwise oxo silylation to form (Me3SiO)2UI2(MesPDIMe) (5) or (Me3SiO)­UI2( t Bu-MesPDIMe) (5- t Bu), respectively. Additional equivalents result in full uranium–oxo bond scission and formation of UI4(1,4-dioxane)2 with extrusion of hexamethyldisiloxane. 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Am. Chem. Soc</addtitle><description>Two uranium­(VI) uranyl compounds, Cp*UO2­(MesPDIMe) (3) and Cp*UO2( t Bu-MesPDIMe) (3- t Bu) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienide; MesPDIMe = 2,6-((Mes)­N=CMe)2C5H3N; t Bu-MesPDIMe = 2,6-((Mes)­N=CMe)2-p-C­(CH3)3C5H2N; Mes = 2,4,6-trimethylphenyl), have been synthesized by addition of N-methylmorpholine N-oxide to trianionic pyridine­(diimine) uranium­(IV) precursors, Cp*U­(MesPDIMe)­(THF) (1), Cp*U­(MesPDIMe)­(HMPA) (1-HMPA), and Cp*U­( t Bu-MesPDIMe)­(THF) (1- t Bu). These uranyl complexes contain singly reduced pyridine­(diimine) ligands suggesting formation occurs via cooperative ligand/metal oxidation. Treating 3 or 3- t Bu with stoichiometric equivalents of Me3SiI results in stepwise oxo silylation to form (Me3SiO)2UI2(MesPDIMe) (5) or (Me3SiO)­UI2( t Bu-MesPDIMe) (5- t Bu), respectively. Additional equivalents result in full uranium–oxo bond scission and formation of UI4(1,4-dioxane)2 with extrusion of hexamethyldisiloxane. 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Am. Chem. Soc</addtitle><date>2015-09-02</date><risdate>2015</risdate><volume>137</volume><issue>34</issue><spage>11115</spage><epage>11125</epage><pages>11115-11125</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Two uranium­(VI) uranyl compounds, Cp*UO2­(MesPDIMe) (3) and Cp*UO2( t Bu-MesPDIMe) (3- t Bu) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienide; MesPDIMe = 2,6-((Mes)­N=CMe)2C5H3N; t Bu-MesPDIMe = 2,6-((Mes)­N=CMe)2-p-C­(CH3)3C5H2N; Mes = 2,4,6-trimethylphenyl), have been synthesized by addition of N-methylmorpholine N-oxide to trianionic pyridine­(diimine) uranium­(IV) precursors, Cp*U­(MesPDIMe)­(THF) (1), Cp*U­(MesPDIMe)­(HMPA) (1-HMPA), and Cp*U­( t Bu-MesPDIMe)­(THF) (1- t Bu). These uranyl complexes contain singly reduced pyridine­(diimine) ligands suggesting formation occurs via cooperative ligand/metal oxidation. Treating 3 or 3- t Bu with stoichiometric equivalents of Me3SiI results in stepwise oxo silylation to form (Me3SiO)2UI2(MesPDIMe) (5) or (Me3SiO)­UI2( t Bu-MesPDIMe) (5- t Bu), respectively. Additional equivalents result in full uranium–oxo bond scission and formation of UI4(1,4-dioxane)2 with extrusion of hexamethyldisiloxane. The uranium complexes have been characterized via multinuclear NMR, vibrational, and electronic absorption spectroscopies and, in some cases, X-ray crystallography.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26299269</pmid><doi>10.1021/jacs.5b06217</doi><tpages>11</tpages></addata></record>
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