Chemie polyfunktioneller Moleküle. 116. Hydrido-, Deuterido-, Thiolato- und Chlororuthenium(II)-Komplexe des Bis(diphenylphosphino)amins

Chemistry of Polyfunctional Molecules. 116 Hydrido-, Deuterido-, Thiolato-, and Chlororuthenium(II) Complexes of Bis(diphenylphosphino)amine Bis(diphenylphosphino)amine, [(C₆H₅)₂P]₂NH (dppa, 1 ), reacts with [Ru(cod)(cot)] (cod = η-1,5-cyclooctadiene, cot = η-1,3,5-cyclooctatriene) ( 2 ) in a molar ratio of 2 : 1 both in a hydrogen or deuterium atmosphere at room temperature to yield cis-[Ru(H)₂(dppa)₂] ( 3 ) and cis-[Ru(D)₂(dppa)₂] ( 3 a ), 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, Me₃CSH, at room temperature results in the formation of cis-[Ru(H)(SCMe₃)(dppa)₂] ( 5 ). Trans-[RuCl₂(dppa)₂] ( 7 ) can be synthesized by the interaction of [RuCl₂(PPh₃)₃] ( 6 ) with one or two equivalents of 1 in CH₂Cl₂ solution. The NMR spectra of 3, 3 a, 4, 5 and 7 are discussed with respect to molecular stereochemistry and hydrogen-halogen exchange under simultaneous cis-trans rearrangement. In addition to ¹H, ²H, ³¹P{¹H}, and ³¹P NMR, the structures of the different complexes were also derived from 1R, Raman, and mass spectra. The NMR spectra simulation of 3 permits detailed assignments of spin-spin coupling constants. Crystals of cis-[Ru(H)(SCMe₃)(dppa)₂] ( 5 ) are monoclinic, space group P2₁/c, with a = 1 179.9(3), b = 2 228.0(4), c = 1 854.8(6) pm, β = 96.23(2)°, Z = 4, and R_w = 0.062. The structural analysis shows that ruthenium is coordinated by two bidentate organophosphine ligands and by one tert-butyl thiolate molecule. The metal bound hydrogen atom was not located. However, in agreement with ¹H NMR, its position is trans to a phosphorus nucleus.