The short-bite aminobis(phosphonite), PhN{P(-OC10H6(mu-S)C10H6O-)}(2) (2), containing a mesocyclic thioether backbone is synthesized by either treating PhN(PCl2)(2) with 2 equiv of thiobis(2,2'-naphthol) or reacting chlorophosphite (-OC10H6(mu-S)C10H6O-)PCl (1) with aniline in the presence of a base. Treatment of 2 with an equimolar amount of Pd(COD)Cl-2 in the presence of H2O affords a P-N-P-bridged and P,S-metalated binuclear complex, [PhN(P(-OC10H6(mu-S)C10H6O-)-kappa P)(2)Pd2Cl2{P(-OC10H6(mu-S)C10H6O-)(O)-kappa P,kappa S}(2)] (3), whereas the same reaction with 2 equiv of Pd(COD)Cl-2 in the presence of H2O and Et3N produces the mononuclear anionic complex [{(-OC10H6(mu-S)C10H6O-)P(O)-kappa P,kappa S}PdCl2](Et3NH) (5). By contrast, reaction of 2 with 2 equiv of Pd(COD)Cl-2 and H2O in the absence of Et3N gives the hydrogen phosphonate coordinated complex [{(-OC10H6(mu-S)C10H6O-)P(OH)}PdCl2] (4) which converts to the anionic complex in solution or in the presence of a base. Compound 2 on treatment with Pt(COD)X-2 (X = Cl or I) afforded P-coordinated four-membered chelate complexes [PhN(P(-OC10H6(mu-S)C10H6O-)-kappa P)(2)PtX2] (6 X = Cl, 7 X = 1). The crystal structures of compounds 2, 3, 5, and 7 are reported. Compound 3 is the first example of a crystallographically characterized binuclear palladium complex containing a bidentate bridging ligand and its hydrolyzed fragments forming metallacycles containing a palladium-phosphorus a bond. All palladium complexes proved to be very good catalysts for the Suzuki-Miyaura and Mizoroki-Heck cross-coupling and amination reactions with excellent turnover numbers (TON up to 1.46 x 10(5) in the case of the Suzuki-Miyaura reaction).