A series of dissymmetric dinuclear complexes were synthesized, as dual site catalysts in ethylene polymerization, by coupling the allylated a-diimine complexes of the metals Ti, Zr, V, Ni and Pd with the ansa-zirconocene complex [C5H4-SiH(Me)-C5H4]ZrCl2 possessing a hydride silane moiety. The different stages of syntheses included the formation of bis(cyclopentadienide)methyl silane which was u...

a series of dissymmetric dinuclear complexes were synthesized, as dual site catalysts in ethylene polymerization,by coupling the allylated a-diimine complexes of the metals ti, zr, v, ni and pd with the ansa-zirconocenecomplex [c5h4-sih(me)-c5h4]zrcl2 possessing a hydride silane moiety. the different stages of syntheses includedthe formation of bis(cyclopentadienide)methyl silane which was util...

Ten years after the discovery of metallocarboranes, this field of chemistry is still advancing at a rapid pace. While the polyhedral expansion of carboranes has proved to be a general method for the synthesis of metallocarboranes, polymetallic compounds may be synthesized by polyhedral expansion of monometallocarboranes, sometimes producing supraicosahedral complexes. The polyhedral contraction...

Treatment of [{Ti(η(5)-C5Me5)(μ-NH)}3(μ3-N)] (1) with zirconium or hafnium tetrachloride adducts [MCl4(thf)2] affords complexes [Cl3M{(μ3-N)(μ3-NH)2Ti3(η(5)-C5Me5)3(μ3-N)}] (M = Zr (2), Hf (3)). Titanium chloride complexes [Cl2Ti{(μ3-N)2(μ3-NH)Ti3(η(5)-C5Me5)3(μ3-N)}] (4) and [(Me2NH)ClTi{(μ3-N)3Ti3(η(5)-C5Me5)3(μ3-N)}] (5) are obtained by reaction of 1 with [TiCl4-x(NMe2)x] (x = 2, 3). The dim...

Complexes featuring lanthanide (Ln)-Si bonds represent a highly neglected research area. Herein, we report a series of open-shell Ln(II+) and Ln(III+) complexes bearing σ-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the Ln(III+) complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dia...

ÐTitanocene(III) chloride and zirconcene(III) chloride are effective and mild reagents for radical generation in organic synthesis. In carbohydrate chemistry, these species are useful for the conversion of glycosyl halides to glycals, and for the stereospeci®c preparation of C-glycosides. In all cases, the 1-glycosyl radical is an active intermediate, generated by reaction of carbohydrate subst...

Neptunium complexes in the formal oxidation states II, III, and IV supported by cyclopentadienyl ligands are explored, and significant differences between Np and U highlighted as a result. A series of neptunium(III) cyclopentadienyl (Cp) complexes [Np(Cp)3], its bis-acetonitrile adduct [Np(Cp)3(NCMe)2], and its KCp adduct K[Np(Cp)4] and [Np(Cp0)3] (Cp0 1⁄4 C5H4SiMe3) have been made and characte...