CHEMISTRY OF POLYFUNCTIONAL MOLECULES .11 6. HYDRIDERUTHENIUM(II), DEUTERIDORUTHENIUM(II),THIOLATORUTHENIUM(II), AND CHLORORUTHENIUM(II) COMPLEXES OF BIS(DIPHENYLPHOSPHINO)AMINE

Bis(diphenylphosphino)amine, [(C6H5)(2)P]2NH (dppa, 1), reacts with [R u(cod)(cot)] (cod = eta-1,5-cyclooctadiene, cot = eta-1,3,5-cyclooctat riene) (2) in a molar ratio of 2:1 both in a hydrogen or deuterium atm osphere at room temperature to yield cis-[Ru(H)(2)(dppa)(2)] (3) and c is-[Ru(D)(2)(dppa)(2)] (3a), respectively. The dihydride complex 3 is very sensitive towards halogenated solvents: dissolution of 3 in CHCl3 or CH2Cl2 produces the monohydride compound trans-[RuCl(H)(dppa)(2)] (4). Treatment of 3 with a threefold excess of tert-butyl mercaptane, Me(3)CSH, at room temperature results in the formation of cis-[Ru(H)(S CMe(3))(dppa)(2)] (5). Trans-[RuCl2(dppa)(2)] (7) can be synthesized b y the interaction of [RuCl2(PPh(3))(3)] (6) with one or two equivalent s of 1 in CH2Cl2 solution. The NMR spectra of 3, 3a, 4, 5 and 7 are di scussed with respect to molecular stereochemistry and hydrogen-halogen exchange under simultaneous cis-trans rearrangement. In addition to H -1, H-2, P-31{H-1}, and P-31 NMR, the structures of the different comp lexes were also derived from IR, Raman, and mass spectra. The NMR spec tra simulation of 3 permits detailed assignments of spin-spin coupling constants. Crystals of cis-[Ru(H)(SCMe(3))(dppa)(2)] (5) are monoclin ic, space group P2(1)/c, with a = 1179.9(3), b = 2228.0(4), c = 1854.8 (6) pm, beta = 96.23(2)degrees, Z = 4, and R(w) = 0.062. The structura l analysis shows that ruthenium is coordinated by two bidentate organo phosphine ligands and by one tert-butyl thiolate molecule. The metal b ound hydrogen atom was not located. However, in agreement with H-1 NMR , its position is trans to a phosphorus nucleus.