660426-80-2Relevant academic research and scientific papers
Synthesis, reactivity and catalytic activity in transfer hydrogenation of ketones of ruthenium(II) and ruthenium(IV) complexes containing the novel N-thiophosphorylated iminophosphorane-phosphine ligands Ph2PCH2P{=NP(=S)(OR)2}Ph2 (R = Et, Ph)
Cadierno, Victorio,Crochet, Pascale,Diez, Josefina,Garcia-Alvarez, Joaquin,Garcia-Garrido, Sergio E.,Garcia-Granda, Santiago,Gimeno, Jose,Rodriguez, Miguel A.
, p. 3240 - 3249 (2007/10/03)
Iminophosphorane-phosphines Ph2PCH2P{=NP(=S)(OR)2}Ph2 (R = Et 1a, Ph 1b) have been prepared by treatment of bis(diphenylphosphino)methane with an equimolar amount of thiophosphorylated azides (RO)2P(=S)N3. Dimers [{Ru(η6-p-cymene)(μ-Cl)Cl}2] and [{Ru(η3:η3-C10H16) (μ-Cl)Cl}2] react with a two-fold excess of 1a,b yielding the neutral complexes [Ru(η6-p-cymene)Cl2 (κ1-P-Ph2PCH2P{=NP(=S)(OR)2} Ph2)] (R = Et 2a, Ph 2b) and [Ru(η3:η3- C10H16)Cl2(κ1-P- Ph2PCH2P{=NP(=S)(OR)2}Ph2)] (R = Et 5a, Ph 5b), respectively. Treatment of 2a,b and 5a,b with one equivalent of AgSbF6 affords the cationic species [Ru(η6-p-cymene) Cl(κ2-P,S-Ph2PCH2P{=NP(=S) (OR)2}-Ph2)][SbF6] (R = Et 3a, Ph 3b) and [Ru(η3:η3-C10H16)Cl (κ2-P,S-Ph2PCH2P{=NP(=S) (OR)2}Ph2)][SbF6] (R = Et 6a, Ph 6b), respectively. The structure of the cation of complex 6a has been confirmed by X-ray crystallography. The preference observed for the κ2-P,S- vs. κ2-P,N- coordination of 1a,b seems to be sterically controlled since theoretical calculations on the models [Ru(η6- C6H6)Cl(κ2-P,N-H2 PCH2P{=NP(=S)(OH)2} H2)]+ A and [Ru(η6-C6H6)Cl(κ2- P,S-H2PCH2P{=NP(=S)(OH)2} H2)]+ B show that isomer A is ca. 5.0 kcal mol-1 more stable than B. Dicationic complexes [Ru (η6-p-cymene)(κ3-P,N,S-Ph2PCH 2P{=NP(=S)(OR)2}Ph2)] [SbF6]2 (R = Et 4a, Ph 4b) and [Ru(η3:η3-C10 H16)-(κ3-P,N,S-Ph2PCH2 P{=NP(=S)(OR)2}Ph2)][SbF6]2 (R = Et 7a, Ph 7b) have been obtained by treating 2a,b and 5a,b, respectively, with two equivalents of AgSbF6. The reactivity of [Ru(η6-p- cymene)(κ3-P,N,S-Ph2PCH2P{=NP(=S)- (OEt)2}Ph2)][SbF6]2 4a towards neutral and anionic ligands has been explored allowing the synthesis of complexes [Ru(η6-p-cymene)(L)(κ2-P,S- Ph2PCH2P{=NP(=S)(OEt)2}Ph2)] [SbF6]2 (L = N≡CMe 8, PMe3 9, PMe2Ph 10, PMePh2 11) and [Ru(η6-p- cymene)X(κ2-P,S-Ph2PCH2P{=NP(=S) (OEt)2}Ph2)][SbF6] (X = Br 12, I 13, N3 14), respectively. The catalytic activity of complexes 2-7a,b in transfer hydrogenation of ketones by propan-2-ol has been also studied.
