First Titanium-Catalyzed anti-1,4-Hydrosilylation of Dienes

1,4-Hydrosilylation of dienes catalyzed by late transition metals constitutes a straightforward access to allylsilanes. However, when unsymmetric dienes are used, it generally leads to a mixture of regioisomers (tail or head products) via Z-specific 1,4-addition. Here we describe the first catalytic anti-1,4-hydrosilylation of dienes using the cheap and stable Cp2TiF2 complex as catalyst. It affords E-allylsilanes in good to excellent yields with an unprecedented regio- and diastereoselectivity. Dehydrogenative double silylation of dienes can be selectively obtained by simply changing the activation protocol of the precatalyst.

Towards a Library of “Early‐Late” Ti–Ru Bimetallic Complexes

A series of new titanocene phosphanes 3–6 have been prepared by replacing both chloride atoms at the titanium atom of the complexes [TiCl2(η5-C5H5){η5-C5H4(CH2)2PR2}] (1: R = Ph; 2: R = Cy) by sodium fluoride or sodium benzoate in two-phase systems. Treatment of these new metalloligands with the binuclear complex [(p-cymene)RuCl2]2 affords the targeted titanocene difluoride and titanocene dibenzoate bimetallic ruthenium complexes 8–11. The first chiral Ti–Ru bimetallic complex 12 bearing a binaphthyloxy ligand at the titanium centre has been synthesised in this way. In each series, an X-ray crystal structure has been determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, …

ATRP of methyl methacrylate catalysed by novel homo- and heterobimetallic ruthenium complexes

ATRP of Methacrylates Catalysed by Homo- and Heterobimetallic Ruthenium Complexes

The catalytic activity of a series of ruthenium-based homo-and heterobimetallic complexes was determined by investigating the atom transfer radical polymerisation of methyl methacrylate. The complexes under investigation were [(arene)Ru(μ-Cl) 3 RuCl(C 2 H 4 )-(L)] (L = PCy 3 or a N-heterocyclic carbene ligand), [(p-cymene )-Ru(/l-Cl) 3 RuCl(=C=CHR)(PCy 3 )] (R = Ph or t-Bu), and [RuCl 2 -(p-cymene) {PCy 2 (CH2) 2 (n 5 -C 5 H 4 )TiX 2 (n 5 -C 5 H 5 )}] (X = Cl, F, and OBz). The catalytic activity of a variety of related [(p-cymene)-ClRu(μ-Cl) 2 Ru(O/\N)(=CHPh)] complexes (O^N is a Schiff base ligand) is also reported. The results clearly demonstrate that the ligands strongly affect the abili…