Half-sandwich complexes of titanium and zirconium with the (diisopropylaminoethyl)cyclopentadienyl ligand - Molecular structure of [((C5H4CH2CH2NCH)(i)Pr-2)ZnCl3](+)Cl-.2CH(3)OH

The synthesis of titanium and zirconium complexes with the donor functionalized 2-(N,N-diisopropylaminoethyl)cyclopentadienyl (CpN) ligand is described. The reaction of TiCl4 with ((C5H4CH2CH2NPr2)-Pr-i)Li leads to the formation of the highly moisture-sensitive half-sandwich complex ((C5H4CH2CH2NPr2)-Pr-1)TiCl3 (1), which easily forms a coordination polymer. Complex 1 reacts with one equivalent of HCl under protonation of the amino group to give the monomeric hydrochloride [(C5H4CH2CH2N(H)Pr-i(2))TiCl3]Cl-+(-) (2), which shows excellent solubility in polar solvents. The compound ((C5H4CH2CH2NPr2)-Pr-i)Ti(NMe2)(3) (3) is prepared by the reaction of Ti(NMe,), with one equivalent of (C5H5CH2CH2NPr2)-Pr-i ((CpH)-H-N). Reaction of 3 with three equivalents of isopropanol affords the isopropoxy derivative ((C5H4CH2CH2NPr2)-Pr-i)Ti((OPr)-Pr-i), (4) in quantitative yield. The reaction of ((C5H4CH2C2NPr2)-Pr-i)Li with Me3SiCl leads to the formation of the Cp-N-transfer reagent ((C5H4CH2CN2NPr2)-Pr-i)SiMe3 (5). The polymeric zirconium compound [((C5H4CH2CH2NPr2)-Pr-i)ZrCl3](x) (6) is synthesized by the reaction of 5 with ZrCl4. 6 reacts with one equivalent of HCl under protonation of the amino group to give the monomeric air- and moisture-stable hydrochloride [(C5H4CH2CH2N(H)Pr-i(2))ZrCl3]Cl-+(-).2CH(2)OH (7). The structure of 7 has been determined by single-crystal X-ray diffractometry. The reaction of 7 with water leads under exchange of the donor ligands to the formation of the air- and water-stable hydrochloride [(C5H4CH2CH2N(H)Pr-i(2))ZrCl3]Cl-+(-).2H(2)O (8). The compound ((C5H4CH2CH2NPr2)-Pr-i)Zr(NMe2)(3) (9) is prepared by the reaction of Zr(NMe2)(4) with one equivalent of (C5H5CH2CH2NPr2)-Pr-i in nearly quantitative yield.