Terminal chalcogenido complexes of zirconium: Syntheses and reactivity of Cp2*Zr(E)(NC5H5) (E = O, S, Se, Te)

Article abstract of DOI:10.1016/S0022-328X(96)06584-9

The terminal zirconium chalcogenido complexes Cp₂* Zr(E)(NC₅H₅) (Cp* = η⁵-C₅Me₅; E = O, S, Se, Te) are conveniently synthesized by the reactions of Cp₂*Zr(CO)₂ with either N₂O or the elemental chalcogen (S, Se, Te) in the presence of pyridine. The [Zr=E] functionalities in these complexes are highly reactive and undergo a variety of 1,2-addition and cycloaddition reactions, resulting in a diverse array of products. For example, reactions of the zirconium oxo complex Cp₂*Zr(O)(NC₅H₅) yield Cp₂*Zr(OH)₂, Cp₂*Zr(η²-O₂CMe)(η¹-OCOMe). Cp₂*Zr(OPh)₂, Cp₂* Zr(OH)(NH₂), Cp₂*Zr(OH)(NHPh), Cp₂*Zr(OH)[η²-N(Ph)NH₂], Cp₂*Zr(H)(OSiH₂Ph), [Cp₂*Zr(H)](μ-O)[Cp₂*Zr(OH)], Cp₂*Zr(OH)[η¹-OC(R)=CH₂] (R = Me, Ph, Bu^t), Cp₂*Zr(OH)I, Cp₂*Zr(OMe)I, Cp₂*Zr(OSiMe₃)C1, Cp₂*Zr[η²-OCH(R)OCH(R)O] (R = H, Prⁱ, Bu^t), and Cp₂*Zr[η²-OC(Ph)NC(Ph)N].