A phosphomide based PNP ligand, 2,6-{Ph2PC(O)}2(C5H3N), showing PP, PNP and PNO coordination modes

A new class of PNP pincer ligands, pyridine-2,6-diylbis(diphenylphosphino)methanone, 2,6-{Ph2PC(O)}2(C5H3N) (1) (hereafter referred to as "bis(phosphomide)"), was prepared by the reaction of picolinoyldichloride with diphenylphosphine in the presence of triethylamine. The bis(phosphomide) 1 shows symmetrical PNP, unsymmetrical PNO and simple bidentate PP coordination modes when treated with various transition metal precursors. The reaction between 1 and [Ru(p-cymene)Cl2]2 in a 1 : 1 molar ratio yielded a binuclear complex [Ru2Cl4(NCCH3)(p-cymene){2,6-{Ph2PC(O)}2(C5H3N)}] (2) containing an unsymmetrical PNO pincer cage around one of the ruthenium centers, whereas the second ruthenium is bonded to the other phosphorus atom along with cymene and two chloride atoms. Symmetrical pincer complexes [RuCl(NCCH3)2{2,6-{Ph2PC(O)}2(C5H3N)}](ClO4) (3), [Ru(η(5)-C5H5){2,6-{Ph2PC(O)}2(C5H3N)}](OTf) (4) and [RhCl{2,6-{Ph2PC(O)}2(C5H3N)}] (5) were obtained in the respective reactions of 1 with [RuCl(NCCH3)2(p-cymene)](ClO4), [Ru(η(5)-C5H5)Cl(PPh3)2] and [Rh(COD)Cl]2. Group 10 metal complexes [NiCl{2,6-{Ph2PC(O)}2(C5H3N)}](BF4) (6), [PdCl{2,6-{Ph2PC(O)}2(C5H3N)}]ClO4 (7) and [PtCl{2,6-{Ph2PC(O)}2(C5H3N)}]ClO4 (8) were obtained by transmetallation reactions of in situ generated Ag(I) salts of 1 with Ni(DME)Cl2 or M(COD)Cl2 (M = Ni, Pd and Pt). The reactions between 1 and CuX or [Cu(NCCH3)4](BF4) produced mononuclear complexes of the type [CuX{2,6-{Ph2PC(O)}2(C5H3N)}] (9, X = Cl; 10, X = Br; 11, X = I), [Cu(NCCH3){Ph2C(O)}2(C5H3N)}](BF4) (12) and [Cu{Ph2C(O)}2(C5H3N)}2](BF4) (13). Similarly, the silver complexes [AgX{2,6-{Ph2PC(O)}2(C5H3N)}] (14, X = ClO4; 15, X = Br) were obtained by the treatment of 1 with AgClO4 or AgBr in 1 : 1 molar ratios. Treatment of 1 with AuCl(SMe2) in 1 : 1 and 1 : 2 molar ratios produced mono- and binuclear complexes, [AuCl{2,6-{Ph2PC(O)}2(C5H3N)}] (16) and [Au2Cl2{2,6-{Ph2PC(O)}2(C5H3N)}] (17), in good yield. The structures of ligand 1 and complexes 2, 5 and 17 were confirmed using single-crystal X-ray diffraction studies. DFT calculations were carried out to gain more insights into the structure and bonding features as well as feasibility of some key chemical transformations.