New 10-membered inorganic heterocyclic diphosphanes, PhN(PX)(2)[(-OC(6)H(2)((T)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)] (x = cl, f). Synthesis and transition metal complexes (molybdenum(0), ruthenium(II), palladium(II), and platinum(II)) of heterocyclic diphosphanes. crystal and molecular structures of the chloro derivative, PhN(PCl)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)], and of a molybdenum(0) complex of the fluoro derivative, [Mo(CO)(3)[eta(3)-PhN(PF)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)]-kappa P,kappa P,kappa S]].

Bis(dichlorophosphino)aniline, PhN(PCl(2))(2), reacts with stoichiometric amounts of 2,2'-thiobis(4,6-di-tert-butylphenol) to afford a 10-membered heterocycle, PhN(PCl)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t))Bu)(2)C(6)H(2)O-)] (1), in high yield. The structure of the heterocycle has been determined by a single-crystal X-ray analysis. The 10-membered heterocycle 1 reacts with SbF(3) to afford the corresponding fluoro derivative 2 in good yield. The compounds 1 and 2 act as tridentate ligands with molybdenum carbonyl derivatives, forming complexes of the type [Mo(CO)(3)[eta(3)-PhN(PX)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)]-kappa P,kappa P,kappa S]] (3 X = Cl, 4 X = F). A crystal structure of the fluoro derivative 4 showed the facial tricarbonyl complex comprising a relatively strain-free tetracyclic structure with molybdenum in an octahedral environment; the two phosphorus and the sulfur centers were the donor atoms. Compound 2 readily reacts with Ru(II), Pd(II), and Pt(II) derivatives to form chelate complexes, demonstrating the eta(2) mode of coordination.