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Synthesis of an Anthracene-Based Macrocyclic Diphosphine Ligand
Organometallics ( IF 2.5 ) Pub Date : 2020-08-28 , DOI: 10.1021/acs.organomet.0c00463 Martin-Louis Y. Riu 1 , Wesley J. Transue 1 , Ioana Knopf 1 , Christopher C. Cummins 1
Organometallics ( IF 2.5 ) Pub Date : 2020-08-28 , DOI: 10.1021/acs.organomet.0c00463 Martin-Louis Y. Riu 1 , Wesley J. Transue 1 , Ioana Knopf 1 , Christopher C. Cummins 1
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The synthesis and coordination chemistry of cis-macrocyclic diphosphine (PhPA)2 (A = C14H10 or anthracene), which features rigid, sterically encumbering groups in its macrocyclic backbone, is reported. Treatment of [EtOP2A2]AlCl4, obtained in 63% yield from dibenzo-7-phosphanorbornadiene EtOPA and aluminum(III) chloride, with 2 equiv of phenylmagnesium chloride gives (PhPA)2 in 59% yield. The purple, pseudo-square-planar nickel dichloride complex [(PhPA)2]NiCl2 was obtained in 89% yield upon combination of (PhPA)2 with (DME)NiCl2 in dichloromethane. By virtue of the ligand backbone, [(PhPA)2]NiCl2 exhibits a large percent buried volume of 61.4%, greater than that of other common chelating diphosphines, and the steric bulk is extended into the axial positions of the square-planar complex, as revealed by a single-crystal X-ray diffraction study. Treatment of this nickel dichloride complex with K[B(C6F5)4] provided a red dimeric, cationic nickel chloride complex. This dimer was isolated in 43% yield and characterized in a single-crystal X-ray diffraction study.
中文翻译：
蒽基大环二膦配体的合成
据报道，顺式-大环二膦（PhP A）2（A = C 14 H 10或蒽）的合成和配位化学在其大环主链中具有刚性的，占空间的基团。用二当量的苯基氯化镁处理由二苯并七-膦基降冰片二烯EtOP A和氯化铝（III）以63％的收率得到的[EtOP 2 A 2 ] AlCl 4，以59％的收率得到（PhP A）2。紫色，伪正方形平面的二氯化镍络合物[（PhP A）2 ] NiCl 2在二氯甲烷中将（PhP A）2与（DME）NiCl 2合并后，产率为89％。借助配体主链，[（PhP A）2 ] NiCl 2的掩埋体积百分比为61.4％，大于其他常见的螯合二膦，并且空间体积扩展到方形平面的轴向位置如单晶X射线衍射研究所揭示的那样。用K [B（C 6 F 5）4 ]处理该二氯化镍配合物可得到红色的二聚阳离子氯化镍配合物。分离出该二聚体，产率为43％，并在单晶X射线衍射研究中表征。
更新日期：2020-08-28
中文翻译：
蒽基大环二膦配体的合成
据报道，顺式-大环二膦（PhP A）2（A = C 14 H 10或蒽）的合成和配位化学在其大环主链中具有刚性的，占空间的基团。用二当量的苯基氯化镁处理由二苯并七-膦基降冰片二烯EtOP A和氯化铝（III）以63％的收率得到的[EtOP 2 A 2 ] AlCl 4，以59％的收率得到（PhP A）2。紫色，伪正方形平面的二氯化镍络合物[（PhP A）2 ] NiCl 2在二氯甲烷中将（PhP A）2与（DME）NiCl 2合并后，产率为89％。借助配体主链，[（PhP A）2 ] NiCl 2的掩埋体积百分比为61.4％，大于其他常见的螯合二膦，并且空间体积扩展到方形平面的轴向位置如单晶X射线衍射研究所揭示的那样。用K [B（C 6 F 5）4 ]处理该二氯化镍配合物可得到红色的二聚阳离子氯化镍配合物。分离出该二聚体，产率为43％，并在单晶X射线衍射研究中表征。
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