Bulky Siloxyaluminum Alkyls as Models for Al2Me6-Treated Silica Gel Surfaces. Characterization of a Dimethylaniline-Stabilized Dimethylaluminum Cation
摘要:
Reaction of a particularly bulky silanol, (2,4,6-Me3C6H2)(3)SiOH, with Al2Me6 gives, instead of the otherwise preferred unreactive binuclear siloxalanes with two siloxy bridges, a binuclear siloxalane with one siloxy and one methyl bridge, Me2Al(mu-OSi(2,4,6-Me3C6H2)(3))(mu-Me)AlMe2. This species reacts with zirconocene dichlorides under chloride/methyl exchange; with the cationizing reagent PhMe2NH+B(C6F5)(4)(-) it forms the B(C6F5)(4)(-) salt of the mononuclear cation AlMe2(NPhMe2)(2)(+).
Bulky Siloxyaluminum Alkyls as Models for Al<sub>2</sub>Me<sub>6</sub>-Treated Silica Gel Surfaces. Characterization of a Dimethylaniline-Stabilized Dimethylaluminum Cation
作者:Olaf Wrobel、Frank Schaper、Hans H. Brintzinger
DOI:10.1021/om030589l
日期:2004.2.1
Reaction of a particularly bulky silanol, (2,4,6-Me3C6H2)(3)SiOH, with Al2Me6 gives, instead of the otherwise preferred unreactive binuclear siloxalanes with two siloxy bridges, a binuclear siloxalane with one siloxy and one methyl bridge, Me2Al(mu-OSi(2,4,6-Me3C6H2)(3))(mu-Me)AlMe2. This species reacts with zirconocene dichlorides under chloride/methyl exchange; with the cationizing reagent PhMe2NH+B(C6F5)(4)(-) it forms the B(C6F5)(4)(-) salt of the mononuclear cation AlMe2(NPhMe2)(2)(+).
Thermally Stable Uranium Dinitrogen Complex with Siloxide Supporting Ligands
作者:Stephen M. Mansell、Joy H. Farnaby、Anne I. Germeroth、Polly L. Arnold
DOI:10.1021/om4003957
日期:2013.8.12
staggered conformation in different crystals. The U–N2–U complex is stable to vacuum and shows high thermal stability, retaining the formally reduced dinitrogen at 100 °C. The parent three-coordinate uranium(III) [UOSi(Mes)3}3] could not be isolated in our hands, with N2-free syntheses affording only uranium(IV) compounds. The rational synthesis and full characterization of two such U(IV) byproducts