Handford Rex C, Wakeham Russell J, Patrick Brian O, Legzdins Peter
Department of Chemistry, The University of British Columbia , Vancouver, British Columbia, Canada V6T 1Z1.
Inorg Chem. 2017 Mar 20;56(6):3612-3622. doi: 10.1021/acs.inorgchem.7b00027. Epub 2017 Mar 2.
Treatment of CHCl solutions of CpM(NO)Cl (Cp = η-C(CH); M = Mo, W) first with 2 equiv of AgSbF in the presence of PhCN and then with 1 equiv of PhPCHCHPPh affords the yellow-orange salts Cp*M(NO)(PhCN)(κ-PhPCHCHPPh) in good yields (M = Mo, W). Reduction of Cp*M(NO)(PhCN)(κ-PhPCHCHPPh) with 2 equiv of CpCo in CH at 80 °C produces the corresponding 18e neutral compounds, CpM(NO)(κ-PhPCHCHPPh) which have been isolated as analytically pure orange-red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf), to solutions of CpM(NO)(κ-PhPCHCHPPh) at room temperature results in the immediate formation of thermally stable CpM(NO→Sc(OTf))(H)(κ-(CH)PhPCHCHPPh) complexes in which one of the phenyl substituents of the PhPCHCHPPh ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF produces the analogous CpM(NO→BF)(H)(κ-(CH)PhPCHCHPPh) complexes. In contrast, B(CF) forms the 1:1 Lewis acid-base adducts, CpM(NO→B(CF))(κ-PhPCHCHPPh) in CHCl at room temperature. Upon warming to 80 °C, CpMo(NO→B(CF))(κ-PhPCHCHPPh) converts cleanly to the orthometalated product CpMo(NO→B(CF))(H)(κ-(CH)PhPCHCHPPh), but CpW(NO→B(CF))(κ-PhPCHCHPPh) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related PhPCHPPh compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.
首先在苯腈存在下，用2当量的AgSbF处理CpM(NO)Cl（Cp = η-C(CH)；M = Mo、W）的氯仿溶液，然后用1当量的PhPCHCHPPh处理，可高产率得到黄色橙色盐Cp*M(NO)(PhCN)(κ-PhPCHCHPPh)（M = Mo、W）。在80℃下，用2当量的CpCo在CH中还原Cp*M(NO)(PhCN)(κ-PhPCHCHPPh)，生成相应的18电子中性化合物CpM(NO)(κ-PhPCHCHPPh)，已分离得到分析纯的橙红色固体。在室温下，向CpM(NO)(κ-PhPCHCHPPh)溶液中加入1当量的路易斯酸Sc(OTf)，会立即形成热稳定的CpM(NO→Sc(OTf))(H)(κ-(CH)PhPCHCHPPh)配合物，其中PhPCHCHPPh配体的一个苯基取代基发生了分子内邻位金属化。以类似的方式，加入BF会生成类似的CpM(NO→BF)(H)(κ-(CH)PhPCHCHPPh)配合物。相比之下，B(CF)在室温下于氯仿中形成1:1的路易斯酸碱加合物CpM(NO→B(CF))(κ-PhPCHCHPPh)。升温至80℃时，CpMo(NO→B(CF))(κ-PhPCHCHPPh)可干净地转化为邻位金属化产物CpMo(NO→B(CF))(H)(κ-(CH)PhPCHCHPPh)，但CpW(NO→B(CF))(κ-PhPCHCHPPh)生成的产物混合物的身份尚待确定。尝试将此化学方法扩展到包括相关的PhPCHPPh化合物，仅取得了有限的成功。所有新配合物均通过常规光谱和分析方法进行了表征，并且大多数配合物的固态分子结构已通过单晶X射线晶体学分析确定。
