Coordination chemistry of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane: preparation and characterization of Ru(II) complexes.
Coordination chemistry of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane: preparation and characterization of Ru(II) complexes.
复制标题
4-甲基-2,6,7-三氧杂-1-磷杂双环[2,2,1]庚烷的配位化学：Ru(II)配合物的制备和表征。
作者：
Evan E. Joslin;Claire L. McMullin;T. Gunnoe;T. Cundari;M. Sabat;W. Myers
配合物 TpRu[P(OCH(2))(2)(OCCH(3)](PPh(3))Cl (2) [Tp = 氢化三(吡唑基)硼酸盐；P(OCH(2))(2)(OCCH(3)) (1) = (4-甲基-2,6,7-三氧杂-1-磷杂双环[2,2,1]庚烷]和 TpRu(L)(PPh(3))Cl [L = P(OCH(2))(3)CEt (3)、PMe(3) (4) 或 P(OMe)(3) (5)]、(η(6)-C(6)H(6))Ru(L)Cl(2) [L = PPh(3) (6)、P(OMe)(3) (7)、PMe(3) (8)、 P(OCH(2))(3)CEt (9)、CO (10) 或 P(OCH(2))(2)(OCCH(3)) (11)] 和 (η(6)-对伞花烃)Ru(L)Cl(2) [L = P(OCH(2))(3)CEt (12), P(OCH(2))(2)(OCCH(3))P(OCH(2))(2)(OCCH(3)) (13)、P(OMe)(3) (14) 或 PPh(3) (15)] 已被合成、分离，并通过 NMR 光谱、循环伏安法、质谱法以及单晶 X 射线衍射（对于某些配合物）进行表征。数据来自 循环伏安法和固态结构已用于比较（1）与其他磷基配体以及一氧化碳的性质。 Ru(II)配合物的固态结构数据表明P(OCH(2))(2)(OCCH(3))的锥角为104°。循环伏安法数据表明 Ru(II) 配合物具有 P(OCH(2))(2)(OCCH(3))比与其他磷配体的类似配合物具有更正的Ru(III/II)氧化还原电位；然而， (η(6)-C(6)H(6))Ru[P(OCH(2))(2)(OCCH(3))]Cl(2) 的 Ru(III/II) 电势比 Ru(III/II) 电势更负 CO络合物(η(6)-C(6)H(6))Ru(CO)Cl(2)。对于本文研究的 Ru(II) 配合物，这些数据与 1 的总体供体能力一致，小于其他常见膦（例如 PMe(3) 或 PPh(3)）或亚磷酸酯 [例如 P(OCH(2))(3)CEt 或 P(OMe)(3)] 但大于碳 一氧化碳。
The complexes TpRu[P(OCH(2))(2)(OCCH(3)](PPh(3))Cl (2) [Tp = hydridotris(pyrazolyl)borate; P(OCH(2))(2)(OCCH(3)) (1) = (4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane] and TpRu(L)(PPh(3))Cl [L = P(OCH(2))(3)CEt (3), PMe(3) (4) or P(OMe)(3) (5)], (η(6)-C(6)H(6))Ru(L)Cl(2) [L = PPh(3) (6), P(OMe)(3) (7), PMe(3) (8), P(OCH(2))(3)CEt (9), CO (10) or P(OCH(2))(2)(OCCH(3)) (11)] and (η(6)-p-cymene)Ru(L)Cl(2) [L = P(OCH(2))(3)CEt (12), P(OCH(2))(2)(OCCH(3))P(OCH(2))(2)(OCCH(3)) (13), P(OMe)(3) (14) or PPh(3) (15)] have been synthesized, isolated, and characterized by NMR spectroscopy, cyclic voltammetry, mass spectrometry, and, for some complexes, single crystal X-ray diffraction. Data from cyclic voltammetry and solid-state structures have been used to compare the properties of (1) with other phosphorus-based ligands as well as carbon monoxide. Data from the solid-state structures of Ru(II) complexes show that P(OCH(2))(2)(OCCH(3)) has a cone angle of 104°. Cyclic voltammetry data reveal that the Ru(II) complexes bearing P(OCH(2))(2)(OCCH(3)) have more positive Ru(III/II) redox potentials than analogous complexes with the other phosphorus ligands; however, the Ru(III/II) potential for (η(6)-C(6)H(6))Ru[P(OCH(2))(2)(OCCH(3))]Cl(2) is more negative compared to the Ru(III/II) potential for the CO complex (η(6)-C(6)H(6))Ru(CO)Cl(2). For the Ru(II) complexes studied herein, these data are consistent with the overall donor ability of 1 being less than other common phosphines (e.g., PMe(3) or PPh(3)) or phosphites [e.g., P(OCH(2))(3)CEt or P(OMe)(3)] but greater than carbon monoxide.