Allyl functionalized phosphinite and phosphonite ligands: Synthesis, transition metal chemistry and orthopalladation reactions

Journal of Chemical Sciences

Susmita Naik¹  Guddekoppa S Ananthnag¹  Maravanji S Balakrishn1¹  Singappagudem Govindaraju¹  Shaikh M Mobin² 

[1] Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400 076, India$$;National Single Crystal X-ray Diffraction Facility, Indian Institute of Technology Bombay, Mumbai 400 076, India$$

关键词: Phosphonites;    palladium(II);    orthopalladation;    orthometallation;    metal complexes;    gold(I) and ruthenium(II) complexes.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

Allyl functionalized phosphinite PPh2(OAr) [Ar=C6H4(𝑜-C3H5)] (1) and phosphonite PPh(OAr)2 (2) ligands were prepared by the reactions of 2-allylphenol with PPh2Cl and PPhCl2, respectively. The ruthenium(II) complexes, [Ru(𝜂6-𝑝-cymene)(PPh2(OAr))Cl2] (3) and [Ru(𝜂6-𝑝-cymene)(PPh(OAr)2Cl2)] (4) were obtained by reacting 1 or 2 with [Ru(𝜂6-𝑝-cymene)Cl2]2 in 2:1 molar ratios, respectively. Reactions of 1 or 2 with AuCl(SMe2) gave [Au{PPh2(OAr)}Cl] (5) or [Au{PPh(OAr)2}Cl] (6) in good yield. The palladium complex, [Pd{PPh(OAr)2}2Cl2] (7) was prepared by reacting Pd(COD)Cl2 with 2 in 1:2 molar ratio. The reaction between Pd(COD)Cl2 and 1 yielded a mixture of orthopalladated cis- and trans-[Pd(Ph2P(OAr))Cl]2 (8a and 8b). The treatment of 8 with PPh3 and Ph2PCH2PPh2 resulted in the cleavage of chloro bridge to give respectively, [Ph2(OAr)PPd(PPh3)Cl] (9) and [Ph2(ArO)PPd(𝜂2-dppm)]OTf (10). Single crystal X-ray structure of the ruthenium complex 3 is described.

【 授权许可】

Unknown