Formation of Novel P-Functionalized Ligands by Insertion Reactions of RNCX (R = Ph, X = O, S; R = Prⁱ, X = O) into the Zr−P Bond of [Cp°₂ZrCl(PHCy)] (Cp° = η⁵-C₅EtMe₄, Cy = Cyclohexyl) and [Cp‘₂ZrCl{PH(TRIP)}] (Cp‘ = η⁵-C₅MeH₄, TRIP = 2,4,6-Prⁱ₃C₆H₂)

[Cp°₂ZrCl(PHCy)] (1; Cp° = η⁵-C₅EtMe₄, Cy = cyclohexyl) and [Cp‘₂ZrCl{PH(TRIP)}] (2; Cp‘ = η⁵-C₅MeH₄,TRIP = 2,4,6-Prⁱ₃C₆H₂) readily insert RNCX (R = Ph, X = S, O; R = Prⁱ, X = O) to give [Cp°₂ZrCl{η²-XC(PHCy)NR}] (X = S, R = Ph (3); X = O, R = Ph (4); X = O, R = Prⁱ (5)) and [Cp‘₂ZrCl{η²-XC{PH(TRIP)}NR}] (X = S, R = Ph (6); X = O, R = Ph (7); X = O, R = Prⁱ (8)). 3−8 were characterized spectroscopically (IR, NMR, MS), and crystal structure determinations on 4−6 showed an η² bonding mode (X,N) of the XC(PHR‘)NR (R‘ = Cy, TRIP) ligands. Of the two possible coordination modes of the ligand, 4 and 5 are obtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr−Cl bond, while for 6−8, both isomers (endo and exo) are formed (1:8 (6), 1:30 (7) and 1:5 (8)), whereby the exo isomer is favored. The exo isomer of 6 was structurally characterized.