Five-coordinate fluorobenzothiolate osmium(IV) complexes [Os(SR _F)_4(PR_3)] (RF = C_6F _4H-4, R_3 = Ph_2(C_6F_5); RF = C_6F_4H-4, R_3 = (OPh) _3; R_F = C_6F_5, R_3 = (OPh)_3)

Cerón M.; Cortina V.; Ramírez-Monroy A.; Berns S.; Torrens H.; Arroyo M.

首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Five-coordinate fluorobenzothiolate osmium(IV) complexes [Os(SR _F)_4(PR_3)] (RF = C_6F _4H-4, R_3 = Ph_2(C_6F_5); RF = C_6F_4H-4, R_3 = (OPh) _3; R_F = C_6F_5, R_3 = (OPh)_3)

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Five-coordinate fluorobenzothiolate osmium(IV) complexes [Os(SR _F)_4(PR_3)] (RF = C_6F _4H-4, R_3 = Ph_2(C_6F_5); RF = C_6F_4H-4, R_3 = (OPh) _3; R_F = C_6F_5, R_3 = (OPh)_3)

机译：五配位氟苯甲硫醇（IV）络合物[Os（SR _F）_4（PR_3）]（RF = C_6F _4H-4，R_3 = Ph_2（C_6F_5）; RF = C_6F_4H-4，R_3 =（OPh）_3; R_F = C_6F_5，R_3 =（OPh）_3）

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Reactions of OsO_4 with excess of HSRF and PR 3 in ethanol afford five-coordinate compounds [Os(SR _F)_4(PR_3)] (R_F = C_6F _4H-4, R_3 = Ph_2(C_6F_5) (1); R_F = C_6F_4H-4, R_3 = (OPh) _3 (2); and R_F = C_6F_5, R_3 = (OPh)_3 (3)). Single crystal X-ray diffraction studies of 1-3 exhibit a common pattern with an osmium center in a trigonal-bipyramidal coordination arrangement. Axial positions are occupied by mutually trans thiolate and phosphine or phosphite ligands, while the remaining three equatorial positions are occupied by thiolate ligands. In compound 1 the tetrafluorophenyl rings of the equatorial ligands are directed away from the axial phosphine ligand in a "3-up" arrangement. In contrast, a "2-up, 1-down" arrangement was found in compounds 2 and 3, where only two of the fluorinated rings from the equatorial thiolates are directed towards the axial thiolate, while the fluorinated substituent of the third equatorial thiolate is directed towards the phosphine ligand. Structural characterization in solution by ~1H, ~(31)P{~1H} and ~(19)F NMR, variable temperature and COSY ~(19)F-~(19)F NMR studies are discussed.

机译：OsO_4与过量的HSRF和PR 3在乙醇中的反应得到五配位化合物[Os（SR _F）_4（PR_3）]（R_F = C_6F _4H-4，R_3 = Ph_2（C_6F_5）（1）; R_F = C_6F_4H-在图4中，R_3 =（OPh）_3（2）;并且R_F = C_6F_5，R_3 =（OPh）_3（3））。 1-3的单晶X射线衍射研究显示出pattern中心处于三角-双锥体配位排列的常见模式。轴向位置被相互反式硫醇盐和膦或亚磷酸酯配体占据，而其余三个赤道位置被硫醇盐配体占据。在化合物1中，赤道基配体的四氟苯环以“ 3-向上”的排列方式从轴向膦配体中引出。相比之下，在化合物2和3中发现“ 2-上，1-下”排列，赤道硫醇盐中只有两个氟化环指向轴向硫醇盐，而第三个赤道硫醇盐的氟化取代基是直接针对膦配体。讨论了溶液的结构表征，包括〜1H，〜（31）P {〜1H}和〜（19）F NMR，可变温度和COZY〜（19）F-〜（19）F NMR研究。

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来源
《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2011年第7期|共8页
作者
Cerón M.; Cortina V.; Ramírez-Monroy A.; Berns S.; Torrens H.; Arroyo M.;
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正文语种 eng
中图分类无机化学;
关键词
Five-coordinate osmium; Fluorinated thiolates; Fluxional processes; Phosphines;

机译：五配位;氟化硫醇盐;通量过程;膦;

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1. Five-coordinate fluorobenzothiolate osmium(IV) complexes [Os(SR _F)_4(PR_3)] (RF = C_6F _4H-4, R_3 = Ph_2(C_6F_5); RF = C_6F_4H-4, R_3 = (OPh) _3; R_F = C_6F_5, R_3 = (OPh)_3) [J] . Cerón M., Cortina V., Ramírez-Monroy A., Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2011,第7期

机译：五配位氟苯甲硫醇（IV）络合物[Os（SR _F）_4（PR_3）]（RF = C_6F _4H-4，R_3 = Ph_2（C_6F_5）; RF = C_6F_4H-4，R_3 =（OPh）_3; R_F = C_6F_5，R_3 =（OPh）_3）

Five-coordinate fluorobenzothiolate osmium(IV) complexes [Os(SR _F)_4(PR_3)] (RF = C_6F _4H-4, R_3 = Ph_2(C_6F_5); RF = C_6F_4H-4, R_3 = (OPh) _3; R_F = C_6F_5, R_3 = (OPh)_3)

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