Tpru hydride and dihydrogen complexes bearing bidentate phosphinoamine ligands. NMR study of proton transfer to [TpRuH(L)] (L = R,R-dippach, dippae; Tp = hydrotris(pyrazolyl)borate)
Tpru hydride and dihydrogen complexes bearing bidentate phosphinoamine ligands. NMR study of proton transfer to [TpRuH(L)] (L = R,R-dippach, dippae; Tp = hydrotris(pyrazolyl)borate)
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带有二齿膦胺配体的 Tpru 氢化物和二氢络合物。
DOI：
10.1021/om050199u
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发表时间：
2005
期刊：
影响因子：
2.8
通讯作者：
P. Valerga
中科院分区：
文献类型：
--
作者：
M. Jiménez;M. Palacios;M. Puerta;P. Valerga
非对映体纯配合物 [TpRuX(R,R-dippach)] (X = Cl (1a), H (2a); R,R-dippach = (R,R)-1,2-双((二异丙基膦基)氨基)环己烷) 以及非手性衍生物 [TpRuX(dippae)] (X = Cl (1b), H (2b); duppae = 1,2-双((二异丙基膦基)氨基)乙烷)已被制备并表征。 1a 或 1b 与 H2 和 NaBAr‘4 (Ar‘ = 3,5-双(三氟甲基)苯基)在氟苯中反应生成相应的稳定二氢配合物 [TpRu(H2)(R,R-dippach)][BAr‘4] (3a) 和 [TpRu(H2)(dippae)][BAr‘4] (3b)。在这些化合物中，没有观察到氨基质子和与金属结合的氢原子之间存在显着的分子内相互作用。 3a 和 3b 都很容易与二氮反应，形成配合物 [TpRu(N2)(R,R-dippach)][BAr'4] (4a) 和 [TpRu(N2)(dippae)][BAr'4] (4b)。测定了3b和4b的X射线晶体结构。通过核磁共振波谱研究了 HBF4·OEt2 在一氢化物 2a 和 2b 上的质子转移过程...
The diastereomerically pure complexes [TpRuX(R,R-dippach)] (X = Cl (1a), H (2a); R,R-dippach = (R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane) as well as the nonchiral derivatives [TpRuX(dippae)] (X = Cl (1b), H (2b); dippae = 1,2-bis((diisopropylphosphino)amino)ethane) have been prepared and characterized. The reaction of either 1a or 1b with H2 and NaBAr‘4 (Ar‘ = 3,5-bis(trifluoromethyl)phenyl) in fluorobenzene yields the corresponding stable dihydrogen complexes [TpRu(H2)(R,R-dippach)][BAr‘4] (3a) and [TpRu(H2)(dippae)][BAr‘4] (3b). No significant intramolecular interaction between the amino protons and the hydrogen atoms bound to the metal has been observed in any of these compounds. Both 3a and 3b react readily with dinitrogen, furnishing the complexes [TpRu(N2)(R,R-dippach)][BAr‘4] (4a) and [TpRu(N2)(dippae)][BAr‘4] (4b). The X-ray crystal structures of 3b and 4b were determined. The proton-transfer processes over the monohydrides 2a and 2b with HBF4·OEt2 have been studied by NMR spectroscopy...