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 ANDC-13 AND P-31 NMR-STUDY OF RELATED PHOSPHORUS COMPLEXES

Reaction of N,N'-bis(tolylsulfonyl)-1,2-diaminoethane with PhPCl(2) gi ves in 62% yield the phosphonous diamide -1,3-bis(p-tolylsulfonyl)-1,3 ,2-diazaphospholidine (4, ''TosL'') and with Ph(2)PCl in 43% yield the diphosphinous amide phino)-N,N'-bis(p-tolylsulfonyl)-1,2-ethanediamin e (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)(4)NO gives c is, cis, trans-(diTosL)W(CO)(2)(NO)Br (8) in 86% yield. The IR, C-13 N MR, and P-31 NMR spectra of 4, 5, 6, and 8 are compared to those of a variety of compounds including LW(CO)(5) (L = PMe(3), PPh(3), PPh(NEt( 2))(2), P(OMe)(3), P(CF3)(3)), L(2)W(CO)(2)(NO)Br (L(2) = Ar(2)PCH(2)C H(2)PATr(2) (Ar = Ph (diphos), C6F5 (diphos-F-20)), (CH3CN)(2)), and t he free ligands as appropriate. The IR data are interpreted to suggest a relative ordering of ligand acceptor ability of P(CF3)(3) > 4 appro ximate to P(OMe)(3) > PPh(3) approximate to PPh(NEt(2))(2) and a relat ive ordering of ligand donor ability of PPh(NEt(2))(2) greater than or equal to P(OMe)(3) > PPh(3) > 4 > P(CF3)(3) The chelating ligand diTo sL is about as electron-withdrawing as diphos-F-20, on the basis of th e IR data. The P-31 NMR data qualitatively support the conclusion that TosL and diTosL are highly electron-withdrawing ligands, on the basis of (I)J(PW). The C-13 data do not permit any such generalizations, al though the spectra of the diphosphine ligands and adducts are of inter est due to the observation of ''virtual coupling'' that surprisingly c an be simulated only as ABX rather than AA'X spin-systems.