Formation of (Alkenylphosphonio)phenylruthenium Complexes from Diphenylacetylene and a [CpRu(dppm)] Cation: Experimental Evidence for the Equilibrium between η1-Disubstituted Vinylidene and η2-Internal Alkyne
Formation of (Alkenylphosphonio)phenylruthenium Complexes from Diphenylacetylene and a [CpRu(dppm)] Cation: Experimental Evidence for the Equilibrium between η1-Disubstituted Vinylidene and η2-Internal Alkyne
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DOI：
10.1021/om3004948
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发表时间：
2012-07
期刊：
影响因子：
2.8
通讯作者：
Y. Mutoh;Yusuke Kimura;Yousuke Ikeda;N. Tsuchida;K. Takano;Y. Ishii
中科院分区：
文献类型：
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作者：
Y. Mutoh;Yusuke Kimura;Yousuke Ikeda;N. Tsuchida;K. Takano;Y. Ishii
研究了二苯乙炔在阳离子Ru(Ph2PCH2PPh2)配体[CpRu(Dppm)]+上的反应，首次揭示了过渡金属中心的η2-内炔和η1-二取代亚乙叉之间存在平衡.反应混合物在70℃下反应69h，意外地得到二苯乙炔与DPPM配体的偶联产物[CpRu{Ph2PCH2P(C6H4)Ph(η2-C(Ph)═CHPh)}]+，其配位方式为κ1P，η1C，η2C，C‘。在对二甲苯回流温度下，(烯基膦)苯基络合物进一步发生了烯烃配位面的反转。对(烯基膦)苯基化合物的两种异构体以及中间体η-2-内炔和η-1-二取代亚乙叉化合物进行了光谱和结晶学的全面表征。考虑到所合成的(烯基膦)苯基配合物的结构，该偶联反应具有较高的选择性。
The reaction of diphenylacetylene at a cationic ruthenium complex with a dppm (Ph2PCH2PPh2) ligand, [CpRu(dppm)]+, has been studied to reveal essentially for the first time the existence of an equilibrium between an η2-internal alkyne and η1-disubstituted vinylidene at a transition metal center. The reaction mixture at 70 °C for 69 h unexpectedly afforded a coupling product of diphenylacetylene and the dppm ligand, an (alkenylphosphonio)phenyl complex [CpRu{Ph2PCH2P(C6H4)Ph(η2-C(Ph)═CHPh)}]+ with the extremely rare coordination mode of κ1P,η1C,η2C,C′. The (alkenylphosphonio)phenyl complex further undergoes inversion of the coordination face of the alkene moiety at p-xylene reflux temperature. Both isomers of (alkenylphosphonio)phenyl complexes as well as the intermediary η2-internal alkyne and η1-disubstituted vinylidene complexes were fully characterized spectroscopically and crystallographically. By considering the structure of the (alkenylphosphonio)phenyl complexes obtained, the coupling reaction has ...