Hydrophilic (η6-Arene)-Ruthenium(II) Complexes with P-OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C-H Bond Arylation Reactions in Water
Hydrophilic (η6-Arene)-Ruthenium(II) Complexes with P-OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C-H Bond Arylation Reactions in Water
复制标题
DOI：
10.1021/acs.organomet.9b00463
复制
发表时间：
2019-10-14
期刊：
影响因子：
2.8
通讯作者：
Cadierno, Victorio
中科院分区：
文献类型：
--
作者：
Gonzalez-Fernandez, Rebeca;Crochet, Pascale;Cadierno, Victorio
含η（6）配位的3-苯丙醇和次膦酸型配体的半夹心钌（II）配合物[RuCl 2（η（6）-C6 H5 CH 2CH 2CH 2 OH）{P（OH）R-2}]（R = Me（2a），Ph（2b），4-C6 H4 CF 3（2c），4-C6 H4 OMe（2d），OMe（2 e），OEt（2f），和OPh（2g），以44-88%产率合成。k（1）（O）-C6 H5 CH 2CH 2CH 2 OH}]（1）与适当的五价磷氧化物R2 P（=O）H反应。[RuCl_2（eta（6）-C_6 H_5CH_2CH_2 OH）{P（OH）Me-2}]（2a）的结构通过X-射线衍射方法明确地证实。化合物2a-g被证明在烯丙基苯异构化成相应的烯丙基苯中具有催化活性。以水为唯一反应溶剂合成的（1-丙烯基）苯衍生物中，[RuCl 2（eta（6）-C6 H5 CH 2CH 2CH 2 OH）{P（OH）（OPh）（2）}]（2g）表现出最好的性能和较宽的底物范围（73-93%的分离产率，E/Z比约为90：10，使用1摩尔%的2g和3摩尔%的K2 CO 3，并在80 ℃下进行催化反应4-24小时）。本文提出的结果首次显示了次膦酸作为金属催化烯烃异构化过程的辅助配体的效用，提出了其中P-OH单元的协同作用的反应。此外，还简要讨论了配合物2a-g作为2-苯基吡啶邻位芳基化反应催化剂的应用。
Half-sandwich ruthenium(II) complexes containing eta(6)-coordinated 3-phenylpropanol and phosphinous-acid-type ligands, namely, [RuCl2(eta(6)-C6H5CH2CH2CH2OH){P(OH)R-2}] (R = Me (2a), Ph (2b), 4-C6H4CF3(2c), 4-C6H4OMe (2d), OMe (2e), OEt (2f), and OPh (2g), have been synthesized in 44-88% yield by reacting [RuCl2 {eta 6:k(1) (O)-C6H5CH2CH2CH2OH}] (1) with the appropriate pentavalent phosphorus oxide R2P(=O)H. The structure of [RuCl2(eta(6)-C6H5CH2CH2CH2OH){P(OH)Me-2}] (2a) was unequivocally confirmed by X-ray diffraction methods. Compounds 2a-g proved to be catalytically active in the isomerization of allylbenzenes into the corresponding (1-propenyl)benzene derivatives employing water as the sole reaction solvent, with [RuCl2(eta(6)-C6H5CH2CH2CH2OH){P(OH)(OPh)(2)}] (2g) showing the best performance and a broad substrate scope (73-93% isolated yields with E/Z ratios around 90:10 employing 1 mol % of 2g and 3 mol % of K2CO3, and performing the catalytic reactions at 80 degrees C for 4-24 h). The results herein presented show for the first time the utility of phosphinous acids as auxiliary ligands for metal-catalyzed olefin isomerization processes, reactions in which a cooperative role for the P-OH unit is proposed. On the other hand, the utility of complexes 2a-g as catalysts for ortho-arylation reactions of 2-phenylpyridine in water is also briefly discussed.