Large bite bisphosphite ligand, 2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2 (2), is obtained by reacting chlorophosphite, {-OC10H6(μ-S)C10H6O-}PCl (1) with 2,6-pyridinedimethanol in presence of triethylamine.Treatment of 2 with aqueous solution of H2O2 or elemental sulfur resulted in the formation of bis(oxide) or bis(sulfide) derivatives, 2,6-C5H3N{CH2OP(E)(–OC10H6)(μ-S)(C10H6O–)}2 (3, E = O; 4, E = S) in quantitative yield.The 10-membered cationic chelate complex, [RuCl(η6-C10H14)η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2-κP,κP]Cl (5) is produced in the reaction between [Ru(p-cymene)(μ-Cl)(Cl)]2 and bisphosphite 2, whereas the neutral chelate complex, cis-[Rh(CO)Cl{2,6-C5H3N{CH2OP(–OC10H6(μ-S)C10H6O–)}2}-κP,κP] (6) is isolated in the reaction of 2 with 0.5 equiv.of [Rh(CO)2Cl]2.Compound 2 on treatment with M(COD)Cl2 (M = Pd, Pt) produce the chelate complexes, [MCl2{η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2}-κP,κP] (7, M = Pd;10, M = Pt).Similarly the reaction of bisphosphite 2 with Pd(COD)MeCl affords cis-[PdMe(Cl)η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2-κP,κP] (8).Treatment of 2 with [Pd(η3- C3H5)Cl]2 in the presence of AgClO4 furnish the cationic complex, [Pd(η3-C3H5)η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2-κP,κP]ClO4 (9). The binuclear complex, [Au2Cl2{2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2}-κP,κP] (11) is obtained in the reaction of compound 2 with two equiv. of AuCl(SMe2), where the ligand exhibits bridged bidentate mode of coordination. All the complexes are characterized by the 1H NMR, 31P NMR, elemental analysis and mass spectroscopy data. The cationic ruthenium complex 5 is proved to be an active catalyst for the hydrogenation of styrene and α-methyl styrene.