Titanium and zirconium complexes of the N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligand: syntheses, structures and uses in catalytic hydrosilylation reactions.

We report here a number of dianionic 1,4-diaza-1,3-butadiene complexes of titanium and zirconium synthesised by a salt metathesis reaction. The reaction of either CpTiCl3 or Cp2TiCl2 with the dilithium salt of N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene [; abbreviated (Dipp)2DADLi2] afforded the mono-cyclopentadienyl titanium complex [η(5)-CpTi((Dipp)2DAD)Cl] () bearing a dianionic ene-diamide ligand, while the analogous reaction of zirconocene dichloride (Cp2ZrCl2) with the dilithium salt gave the bis-cyclopentadienyl zirconium complex [Cp2Zr{(Dipp)2DAD}] (). The metal dichloride complexes [Ti((Dipp)2DAD)Cl2] () and [{(Dipp)2DADZrCl(µ-Cl)}2(κ(3)-Cl)(Li)(OEt2)2] () were obtained by the reaction of and anhydrous metal tetrachloride in a 1 : 1 molar ratio in diethyl ether at room temperature. Meanwhile, the homoleptic titanium complex [Ti{((Dipp)2DAD)}2] () was isolated in good yield by the treatment of with TiCl4 in a 1 : 2 molar ratio in diethyl ether. The complexes and were further reacted with neosilyl lithium to afford mono- and bis-alkyl complexes of titanium [η(5)-CpTi{(Dipp)2DAD}(CH2SiMe3)] () and zirconium [Zr{(Dipp)2DAD}(CH2SiMe3)2] () respectively. Molecular structures of the complexes , , and in the solid states were confirmed by single crystal X-ray diffraction analysis. The solid state structures of all the complexes reveal that the metal ions are chelated through the amido-nitrogen atoms and the olefinic carbons of the [(Dipp)2DAD](2-) moiety, satisfying the σ(2),π coordination mode. Compound was used as a catalyst for the intermolecular hydrosilylation reaction of a number of olefins, and moderate activity of catalyst was observed.

Bis(phosphinoselenoic amides) as versatile chelating ligands for alkaline earth metal (Mg, Ca, Sr and Ba) complexes: syntheses, structure and ε-caprolactone polymerisation.

We report here a series of heavier alkaline earth metal complexes with N,N'-(ethane-1,2-diyl)bis(P,P-diphenylphosphinoselenoic amide) using two synthetic routes. In the first route, the heavier alkaline earth metal bis(trimethylsilyl)amides [M{N(SiMe3)2}2(THF)n] (M = Ca, Sr, Ba), when treated with phosphinoselenoic amine [Ph2P(Se)NHCH2CH2NHPPh2(Se)] (1), afforded the corresponding alkaline earth metal complexes of the composition [(THF)3M{Ph2P(Se)NCH2CH2NPPh2(Se)}] [M = Ca (2), Sr (3), Ba (4)]. The metal complexes 2-4 were also obtained from a one-pot reaction, where potassium phosphinoselenoic amide was generated in situ by the reaction of compound 1 and [KN(SiMe3)2], followed by the addition of the respective metal diiodides in THF at room temperature. The magnesium complex [(THF)3Mg{Ph2P(Se)NCH2CH2NPPh2(Se)}] (5) was also prepared. The solid-state structures of alkaline earth metal complexes 2-5 were established by single crystal X-ray diffraction analysis. In the solid state, all the metal complexes are monomeric but in complexes 2-4, ligand 1 is chelated in a tetra-dentate fashion to each metal ion but in complex 5, ligand 1 behaves as a bidentate ligand. Complexes 2-4 were tested as catalysts for the ring-opening polymerisation of ε-caprolactone and a high level of activity for the barium complex 4 was observed, with narrow polydispersity. We also report the synthesis and structure of the bis(amidophosphino borane) ligand [Ph2P(BH3)NHCH2CH2NHPPh2(BH3)] (6) and the corresponding barium complex [(THF)2Ba{Ph2P(BH3)NCH2CH2NPPh2(BH3)}]2 (7).