期刊
RSC ADVANCES
卷 12, 期 8, 页码 4510-4520出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ra08961g
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资金
- SERB (DST, New Delhi, India) [CRG/2021/000298]
- CSIR (New Delhi, India)
This article reports a new method for the synthesis of phosphonite compounds and transition metal complexes, and verifies its importance through the study of the structures of the products and catalytic reactions.
The reaction of Ph2PCH2OH with PhPCl2 and PCl3 in the presence of Et3N afforded new phosphonite compounds PhP(OCH2PPh2)(2)1 and P(OCH2PPh2)(3)2, respectively. The reaction between 1 and [NiCl2(DME)] in dichloromethane gave the five-coordinate complex [NiCl2(1-kappa P-3,P,P)] 3. Conversely, 1 reacts with [NiCl2(DME)] in the presence of NH4PF6 in dichloromethane to yield the four coordinate ionic complex [NiCl(1-kappa P-3,P,P)][PF6] 4. The reactions between 1, [NiCl2(DME)] and KPF6 in the presence of RNC (R = Xylyl, Bu-t and Pr-i) in dichloromethane yielded the five coordinate monocationic [NiCl(1-kappa P-3,P,P)(RNC)][PF6] (R = Xylyl) and dicationic [Ni(1-kappa P-3,P,P)(RNC)(2)][PF6](2) (R = Bu-t and Pr-i) complexes, respectively. The analogous reaction of 2 with [NiCl2(DME)] in the presence of KPF6 gave complex [NiCl(2-kappa P-4,P,P,P)][PF6], 8. The structures of all complexes were determined by single crystal X-ray diffraction studies and supported by spectroscopic methods. To demonstrate their catalytic application, N-alkylation reactions between primary aryl amines, benzyl and 4-methoxy benzyl alcohols were found to proceed smoothly in the presence of 2.5 mol% of complexes bearing ligand 1 and <0.5 mmol of KOBut in toluene at 140 degrees C. The C-N coupled products were formed in very good yields. Its substrate scope includes sterically encumbered, heterocyclic amines and aliphatic alcohol.
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