New 10-Membered Inorganic Heterocyclic Diphosphanes, PhN(PX)2{(−OC6H2(tBu)2)(μ-S)((tBu)2C6H2O−)} (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{(−OC6H2(tBu)2)(μ-S)((tBu)2C6H2O−)}, and of a Molybdenum(0) Complex of the Fluoro Derivative, [Mo(CO)3{η3-PhN(PF)2{(−OC6H2(tBu)2)(μ-S)((tBu)2C6H2O−)}-κP,κP,κS}]

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.