Synthesis of Tungsten Carbonyl and Nitrosyl Complexes of Monodentate and Chelating Aryl-N-sulfonylphosphoramides, the First Members of a New Class of Electron-Withdrawing Phosphine Ligands. Comparative IR and 13C and 31P NMR Study of Related Phosphorus Complexes

Reaction of N,N‘-bis(tolylsulfonyl)-1,2-diaminoethane with PhPCl2 gives in 62% yield the phosphonous diamide 2-phenyl-1,3-bis(p-tolylsulfonyl)-1,3,2-diazaphospholidine (4, “TosL”) and with Ph2PCl in 43% yield the diphosphinous amide N,N‘-bis(diphenylphosphino)-N,N‘-bis(p-tolylsulfonyl)-1,2-ethanediamine (5, “diTosL”). Reaction of 4 with (THF)W(CO)5 gives (TosL)W(CO)5 (6) in 77% yield, and reaction of 5 with trans-BrW(CO)4NO gives cis, cis, trans-(diTosL)W(CO)2(NO)Br (8) in 86% yield. The IR, 13C NMR, and 31P NMR spectra of 4, 5, 6, and 8 are compared to those of a variety of compounds including LW(CO)5 (L = PMe3, PPh3, PPh(NEt2)2, P(OMe)3, P(CF3)3), L2W(CO)2(NO)Br (L2 = Ar2PCH2CH2PAr2 (Ar = Ph (diphos), C6F5 (diphos-F20)), (CH3CN)2), and the free ligands as appropriate. The IR data are interpreted to suggest a relative ordering of ligand acceptor ability of P(CF3)3 > 4 ≈ P(OMe)3 > PPh3 ≈ PPh(NEt2)2 and a relative ordering of ligand donor ability of PPh(NEt2)2 ≥ P(OMe)3 > PPh3 > 4 > P(CF3)3. The chelating ...