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° 2 ZrCl(PHCy)] ( 1; Cp° = η 5 -C 5 EtMe 4, Cy = cyclohexyl) and [Cp‘ 2 ZrCl{PH(TRIP)}] ( 2; Cp‘ = η 5 -C 5 MeH 4,TRIP = 2,4,6-Pr i 3 C 6 H 2 ) readily insert RNCX (R = Ph, X = S, O; R = Pr i, X = O) to give [Cp° 2 ZrCl{η 2 -XC(PHCy)NR}] (X = S, R = Ph ( 3 ); X = O, R = Ph ( 4 ); X = O, R = Pr i ( 5 )) and [Cp‘ 2 ZrCl{η 2 -XC{PH(TRIP)}NR}] (X = S, R = Ph ( 6 ); X = O, R = Ph ( 7 ); X = O, R = Pr i ( 8 )). 3 − 8 were characterized spectroscopically (IR, NMR, MS), and crystal structure determinations on 4 − 6 showed an η 2 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.