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

作者：Govindaraju Singappagudem; Ananthnag Guddekoppa S; Naik Susmita; Mobin Shaikh M; Balakrishna Maravanji S^*

来源：Journal of Chemical Sciences, 2012, 124(4): 773-779.

DOI：10.1007/s12039-012-0279-4

• Phosphonites
• palladium(II)
• orthopalladation
• orthometallation
• metal complexes
• gold( I) and ruthenium(II) complexes

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(eta (6)-p-cymene)(PPh2(OAr))Cl-2] (3) and [Ru(eta (6)-p-cymene)(PPh(OAr)(2)Cl-2)] (4) were obtained by reacting 1 or 2 with [Ru(eta (6)-p-cymene)Cl-2](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)}(2)Cl-2] (7) was prepared by reacting Pd(COD)Cl-2 with 2 in 1:2 molar ratio. The reaction between Pd(COD)Cl-2 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, [Ph-2(OAr)PPd(PPh3)Cl] (9) and [Ph-2(ArO)PPd(eta (2)-dppm)]OTf (10). Single crystal X-ray structure of the ruthenium complex 3 is described.

• 出版日期2012-7