含有κ1-P-、κ2-P,O-和κ3-P,N,O-亚氨基膦烷-膦配体Ph2PCH2P[=NP(=O)(OR)2]Ph2（R = 乙基、苯基）的钌（II）和钌（IV）配合物：环己酮转移氢化反应中的合成、反应性、理论研究及催化活性
Ruthenium(II) and ruthenium(IV) complexes containing kappa1-P-, kappa2-P,O-, and kappa3-P,N,O-iminophosphorane-phosphine ligands Ph2PCH2P[=NP(=O)(OR)2]Ph2 (R = Et, Ph): synthesis, reactivity, theoretical studies, and catalytic activity in transfer hydrogenation of cyclohexanone.
作者信息
Cadierno Victorio, Crochet Pascale, Díez Josefina, García-Alvarez Joaquín, García-Garrido Sergio E, Gimeno José, García-Granda Santiago, Rodríguez Miguel A
机构信息
Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica "Enrique Moles" (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, E-33071 Oviedo, Spain.
出版信息
Inorg Chem. 2003 May 19;42(10):3293-307. doi: 10.1021/ic020702k.
[(Ru(eta(6)-p-cymene)(mu-Cl)Cl)(2)] and [(Ru(eta(3):eta(3)-C(10)H(16))(mu-Cl)Cl)(2)] react with Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2) (R = Et (1a), Ph (1b)) affording complexes [Ru(eta(6)-p-cymene)Cl(2)(kappa(1)-P-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))] (R = Et (2a), Ph (2b)) and [Ru(eta(3):eta(3)-C(10)H(16))Cl(2)(kappa(1)-P-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))] (R = Et (6a), Ph (6b)). While treatment of 2a with 1 equiv of AgSbF(6) yields a mixture of [Ru(eta(6)-p-cymene)Cl(kappa(2)-P,O-Ph(2)PCH(2)P[=NP(=O)(OEt)(2)]Ph(2))][SbF(6)] (3a) and [Ru(eta(6)-p-cymene)Cl(kappa(2)-P,N-Ph(2)PCH(2)P[=NP(=O)(OEt)(2)]Ph(2))][SbF(6)] (4a), [Ru(eta(6)-p-cymene)Cl(kappa(2)-P,O-Ph(2)PCH(2)P[=NP(=O)(OPh)(2)]Ph(2))][SbF(6)] (3b) and [Ru(eta(3):eta(3)-C(10)H(16))Cl(kappa(2)-P,O-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))][SbF(6)] (R = Et (7a), Ph (7b)) are selectively formed from 2b and 6a,b. Complexes [Ru(eta(6)-p-cymene)(kappa(3)-P,N,O-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))]SbF(6) (R = Et (5a), Ph (5b)) and [Ru(eta(3):eta(3)-C(10)H(16))(kappa(3)-P,N,O-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))]SbF(6) (R = Et (8a), Ph (8b)) have been prepared using 2 equiv of AgSbF(6). The reactivity of 3-5a,b has been explored allowing the synthesis of [Ru(eta(6)-p-cymene)X(2)(kappa(1)-P-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))] (R = Et, Ph; X = Br, I, N(3), NCO (9-12a,b)). The catalytic activity of 2-8a,b in transfer hydrogenation of cyclohexanone, as well as theoretical calculations on the models [Ru(eta(6)-C(6)H(6))Cl(kappa(2)-P,N-H(2)PCH(2)P[=NP(=O)(OH)(2)]H(2))]+ and [Ru(eta(6)-C(6)H(6))Cl(kappa(2)-P,O-H(2)PCH(2)P[=NP(=O)(OH)(2)]H(2))]+, has been also studied.
[(Ru(η⁶ - 对异丙基苯)(μ - Cl)Cl)₂]和[(Ru(η³:η³ - C₁₀H₁₆)(μ - Cl)Cl)₂]与Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂（R = 乙基 (1a)，苯基 (1b)）反应，生成配合物[Ru(η⁶ - 对异丙基苯)Cl₂(κ¹ - P - Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂)]（R = 乙基 (2a)，苯基 (2b)）和[Ru(η³:η³ - C₁₀H₁₆)Cl₂(κ¹ - P - Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂)]（R = 乙基 (6a)，苯基 (6b)）。用1当量的AgSbF₆处理2a会生成[Ru(η⁶ - 对异丙基苯)Cl(κ² - P,O - Ph₂PCH₂P[=NP(=O)(OEt)₂]Ph₂)][SbF₆] (3a)和[Ru(η⁶ - 对异丙基苯)Cl(κ² - P,N - Ph₂PCH₂P[=NP(=O)(OEt)₂]Ph₂)][SbF₆] (4a)的混合物，而[Ru(η⁶ - 对异丙基苯)Cl(κ² - P,O - Ph₂PCH₂P[=NP(=O)(OPh)₂]Ph₂)][SbF₆] (3b)和[Ru(η³:η³ - C₁₀H₁₆)Cl(κ² - P,O - Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂)][SbF₆]（R = 乙基 (7a)，苯基 (7b)）是由2b和6a,b选择性形成的。配合物[Ru(η⁶ - 对异丙基苯)(κ³ - P,N,O - Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂)][SbF₆]₂（R = 乙基 (5a)，苯基 (5b)）和[Ru(η³:η³ - C₁₀H₁₆)(κ³ - P,N,O - Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂)][SbF₆]₂（R = 乙基 (8a)，苯基 (8b)）是使用2当量的AgSbF₆制备的。已经探索了3 - 5a,b的反应活性，从而合成了[Ru(η⁶ - 对异丙基苯)X₂(κ¹ - P - Ph₂PCH₂P[=NP(=O)(OR)₂]Ph₂)]（R = 乙基、苯基；X = 溴、碘、叠氮基、异氰酸根 (9 - 12a,b)）。还研究了2 - 8a,b在环己酮转移氢化反应中的催化活性，以及对模型[Ru(η⁶ - C₆H₆)Cl(κ² - P,N - H₂PCH₂P[=NP(=O)(OH)₂]H₂)]⁺和[Ru(η⁶ - C₆H₆)Cl(κ² - P,O - H₂PCH₂P[=NP(=O)(OH)₂]H₂)]⁺的理论计算。
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