A series of bi- and tri-dentate amido phosphine ligands H[Ph-PNP] (bis(2-diphenylphosphinophenyl)amine), H[iPr-PNP] (bis(2-diisopropylphosphino-
phenyl)amine), H[Cy-PNP] (bis(2-dicyclohexylphosphinophenyl)amine), H[iPr-NP] (N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline), and H[Me-NP] (N-(2-diphenylphosphinophenyl)-2,6-dimethylaniline) have been synthesized in high yield. Lithiation of these compounds with n-BuLi in ethereal solutions afforded the corresponding lithium complexes. The metathetical reactions of MCl4(THF)2 (M = Zr, Hf) with [iPr-NP]Li(THF)2 or [Me-NP]Li(THF)2 in toluene produced the corresponding [iPr-NP]MCl3(THF) and [Me-NP]2MCl2, respectively, in high yield. In contrast, attempts to prepare [Me-NP]MCl3(THF) and [iPr-NP]2MCl2 led to the concomitant formation of mono- and bis-ligated complexes, from which purification proved rather ineffective. The solution and solid-state structures of [iPr-NP]MCl3(THF) and [Me-NP]2MCl2 were studied by multinuclear NMR spectroscopy and X-ray crystallography. Treatment of PdCl2(PhCN)2 with [iPr-NP]Li(THF)2 in THF afforded dimeric {[iPr- NP]PdCl}2, which was reacted with tricyclohexylphosphine to produce [iPr-NP]PdCl(PCy3). The two phosphorus donors in [iPr-NP]PdCl(PCy3) are mutually cis as indicated by the solution NMR and X-ray crystallographic studies. Both {[iPr-NP]PdCl}2 and [iPr-NP]PdCl(PCy3) are highly active catalyst precursors for Suzuki coupling reactions of a wide array of aryl halides, including those featuring electronically deactivated and sterically hindered characteristics. The metathetical reaction of NiCl2(DME) (DME = dimethoxyethane) with [iPr-PNP]Li(THF) and [Cy-PNP]Li(THF), respectively, produced the diamagnetic nickel complexes [iPr-PNP]NiCl and [Cy-PNP]NiCl. These nickel chloride complexes were reacted with Grignard reagents to afford thermally stable nickel alkyl and aryl complexes [iPr-PNP]NiR and [Cy-PNP]NiR (R = Me, Et, n-Bu, Ph). A series of divalent nickel alkoxo, amido, thiolate complexes [iPr-PNP]NiX and [Cy-PNP]NiX (X = OPh, NHPh, SPh) were also easily prepared. Reaction of H[Ph-PNP] with Ni(COD)2 (COD = cycloocta-1,5-diene) produced the transient [Ph-PNP]NiH, which underwent COD insertion to give [Ph-PNP]Ni(£b1- cyclooctenyl). Instead, reactions of Ni(COD)2 with H[iPr-PNP] and H[Cy-PNP], respectively, afforded isolable diamagnetic complexes [iPr-PNP]NiH and [Cy-PNP]NiH without alkene insertion. The reactivity of these nickel hydride complexes was investigated.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0906105-160622 |
| Date | 06 September 2005 |
| Creators | Chien, Pin-Shu |
| Contributors | Teng-yuan Dong, Liang-shiu Lee, Lan-Chang Liang, Yen-Nan Chiang, Tsu-hsin Chang |
| Publisher | NSYSU |
| Source Sets | NSYSU Electronic Thesis and Dissertation Archive |
| Language | Cholon |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0906105-160622 |
| Rights | not_available, Copyright information available at source archive |
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