HETERODIFUNCTIONAL LIGANDS DERIVED FROM MONOOXIDIZED BIS(PHOSPHINO)AMINES - SYNTHESIS AND TRANSITION-METAL (MOLYBDENUM(0), TUNGSTEN(0), RHODIUM(I), PALLADIUM(II), AND PLATINUM(II)) COMPLEXES OF (DIPHENYLPHOSPHINO)(DIPHENYLPHOSPHINOTHIOYL)- AND LPHOSPHINO)(DIPHENYLPHOSPHINOSELENOYL)PHENYLAMINE, PH(2)PN(PH)P(E)PH(2) (E=S, SE) - CRYSTAL AND MOLECULAR-STRUCTURE OF THE PT(II) COMPLEX [CL(2)PTPPH(2)N(PH)P(S)PH(2)]CENTER-DOT-H2O

Bis(diphenylphosphino)phenylamine can be selectively oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoy l products Ph(2)PN(Ph)PPh(2)=E, (E = S, Se). These compounds act as bi dentate chelate ligands toward metal complexes forming (CO)(4)M(LL) (M = Mo, W), CO(Cl)Rh(LL), and Cl(2)M(LL), (M = Pt, Pd) where (LL) is th e thioyl or selenoyl derivative of the aminobis(phosphine). IR and NMR data are given for all complexes. The carbonyl infrared stretching fr equencies show that the chelates form with the phosphine cis to any CO which is present. The P-31 NMR of all complexes consists of two doubl ets except for the Rh complexes wherein the Ph spin also couples to ph osphorus to produce two doublets of doublets. The (2)J(pp) values rang e from 56 to 112 Hz. (1)J(PSe) coupling provide valuable assistance fo r the assignment of the phosphorus resonances which range widely from 55 to 126 ppm for P-III and from 60 to 80 ppm for the P-V case. Assign ment of P-III and P-V signals, which invert relative shift positions o n occasion, is aided by the analysis of appropriate spin satellites ar ising from the substituents. It is concluded that coordination shifts for P-III are always positive, ranging from 22 ppm for Pt-II complexes to 70 ppm for Rh-I complexes. Coordination shifts for P-V centers are much smaller, e.g. 0-12 ppm, and in some cases the coordination shift s for the P-V centers are negative versus the free ligand. A crystal s tructure of the Pt complex [Cl(2)PtPPh(2)N(Ph)P(S)Ph(2)].H2O (at 25 de grees degrees C, monoclinic P2(1)/c a = 9.117(1) Angstrom, b = 18.783( 3) Angstrom, c = 17.288(2) Angstrom, beta = 92.16(1)degrees, V = 2959( 1) Angstrom(3), Z = 4) showed the chelate structure comprising a relat ively strain-free five membered ring containing a trigonal planar N in the backbone. The short P-V(1)-N (1.674(7) Angstrom) bond length is s imilar to a phosphazene bond length and indicative of multiple bond ch aracter. Although the complex could only be crystallized with 1 mol of H2O, there was no evidence for unusual interaction of this water mole cule with the complex. The P-III-N bond length (1.737(7) Angstrom) is similar to the usual P-III-N distances. The geometry suggests signific ant delocalization from the nitrogen bridge into the backbone of the c helate.