Formation of Novel P - Functionalized Ligands by Insertion Reactions of RNCX (R = Ph, X = O, S; R = Pr i , X = O) into the Zr−P Bond of [Cp° 2 ZrCl(PHCy)] (Cp° = η 5 -C 5 EtMe 4 , Cy = Cyclohexyl) and [Cp‘ 2 ZrCl{PH(TRIP)}] (Cp‘ = η 5 -C 5 MeH 4 , TRIP = 2,4,6-Pr i 3 C 6 H 2 )
2000; American Chemical Society; Volume: 19; Issue: 13 Linguagem: Inglês
10.1021/om000170k
ISSN1520-6041
AutoresU. Segerer, Joachim Sieler, Evamarie Hey‐Hawkins,
Tópico(s)Synthesis and characterization of novel inorganic/organometallic compounds
Resumo[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.
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