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
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- 作者：Ulrike Segerer ; Joachim Sieler ; and Evamarie Hey-Hawkins
- 刊名：Organometallics
- 出版年：2000
- 出版时间：June 26, 2000
- 年：2000
- 卷：19
- 期：13
- 页码：2445 - 2449
- 全文大小：117K
- 年卷期：v.19,no.13(June 26, 2000)
- ISSN：1520-6041
文摘
[Cp
2ZrCl(PHCy)] (1; Cp = 
5-C5EtMe4, Cy = cyclohexyl) and [Cp'2ZrCl{PH(TRIP)}] (2;Cp' = 5-C5MeH4,TRIP = 2,4,6-Pri3C6H2) readily insert RNCX (R = Ph, X = S, O; R = Pri,X = O) to give [Cp2ZrCl{2-XC(PHCy)NR}] (X = S, R = Ph (3); X = O, R = Ph (4); X = O,R = Pri (5)) and [Cp'2ZrCl{2-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 crystalstructure determinations on 4-6 showed an 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 areobtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Clbond, 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.
2ZrCl(PHCy)] (1; Cp = 5-C5EtMe4, Cy = cyclohexyl) and [Cp'2ZrCl{PH(TRIP)}] (2;Cp' = 5-C5MeH4,TRIP = 2,4,6-Pri3C6H2) readily insert RNCX (R = Ph, X = S, O; R = Pri,X = O) to give [Cp2ZrCl{2-XC(PHCy)NR}] (X = S, R = Ph (3); X = O, R = Ph (4); X = O,R = Pri (5)) and [Cp'2ZrCl{2-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 crystalstructure determinations on 4-6 showed an 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 areobtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Clbond, 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.