Pentamethylcyclopentadienyl-aminoborole derivatives of zirconium and hafnium with alkyl and allyl ligands

The preparations of new alkyl, iodo, and allyl derivatives of zirconium and hafnium with pentamethylcyclopentadienyl and aminoborole ancillary ligands are described. The dialkyl complexes Cp * {eta(5)-C4H4BN(CHMe(2))(2))ZrR(2)Li (R = Me, C = C-p-C6H4CH3, C = CMe(3), CH(2)Ph) are prepared from Cp * (eta(5)-C4H4BN(CHMe(2))(2)}ZrCl . LiCl and two equivalents of RLi. Cp * ZrI3 is prepared from Cp * ZrCl3 and BI3. Treatment of Cp * ZrI3 with Li-2(THF)(C4H4BN(CHMe(2))(2)} yields Cp * (eta(5)-C4H4BN(CHMe(2))(2))ZrI . LiI(THF). Treatment of Cp * (eta(5)-C4H4BN(CHMe(2))(2)MCl . LiCl (M = Zr, Hf) with allyl magnesium bromide yields Cp * (eta(5)- C(4)Me(4)BN(CHMe(2))(2)}M(eta(3)-C3H5) (M = Zr, Hf). Addition of donor ligands to Cp * (eta(5)-C4H4BN(CHMe(2))(2))Hf(eta(3)-C3H5) yields Cp * (eta(5)-C4H4BN(CHMe(2))(2)}Hf(eta(3)-C3H5)(L) (L = PMe(3), CO) and Cp * (eta(5)-C4H4BN(CHMe(2))(2)}Hf(eta(1)-C3H5)(py). The results of X-ray structure determinations for Cp * (eta(5)-C4H4BN(CHMe(2))(2)Hf(eta(3)-C3H5) and Cp * (eta(5)-C4H4BN(CHMe(2))(2)}Hf(eta(3)-C3H5)(CO) are reported.