Synthesis of High-Oxidation-State MoCHX Complexes, Where X = Cl, CF3, Phosphonium, CN

Reactions between (Z)-XCHCHX, where X = Cl, CF3, CN, and Mo­(N-t-Bu)­(CH-t-Bu)­(OHIPT)­Cl­(PPh2Me) (OHIPT = O-2,6-(2,4,6-i-Pr3C6H2)2C6H3) produce Mo­(N-t-Bu)­(CHX)­(OHIPT)­Cl­(PPh2Me) complexes. Addition of 2,2′-bipyridyl (Bipy) yields Mo­(N-t-Bu)­(CHX)­(OHIPT)­Cl­(Bipy) complexes, which could be isolated and structurally characterized. The reaction between Mo­(N-t-Bu)­(CH-t-Bu)­(OHMT)­Cl­(PPh2Me) (OHMT = O-2,6-(2,4,6-Me3C6H2)2C6H3) and (Z)-ClCHCHCl in the presence of Bipy produces a mixture that contains both Mo­(N-t-Bu)­(CHCl)­(OHMT)­Cl­(PPh2Me) and Mo­(N-t-Bu)­(CHCl)­(OHMT)­Cl­(Bipy), but the relatively insoluble product that crystallizes from toluene-d8 is the phosphoniomethylidene complex [Mo­(N-t-Bu)­(CHPPh2Me)­(OHMT)­Cl­(Bipy)]­Cl. The Mo­(N-t-Bu)­(CHX)­(OHIPT)­Cl­(PPh2Me) complexes (X = Cl, CF3) were confirmed to initiate the stereoselective cross-metathesis between (Z)-5-decene and (Z)-XCHCHX.

本数据集涉及的化学反应与配合物如下：(Z)-XCH=CHX（X=Cl、CF3、CN）与Mo(N-叔丁基)(亚叔丁基)(OHIPT)Cl(PPh2Me)配合物反应，其中OHIPT为O-2,6-(2,4,6-三异丙基苯基)苯基（分子式为O-2,6-(2,4,6-i-Pr3C6H2)2C6H3），PPh2Me为甲基二苯基膦，生成Mo(N-叔丁基)(CHX)(OHIPT)Cl(PPh2Me)配合物。向反应体系中加入2,2'-联吡啶(Bipy)，可得到Mo(N-叔丁基)(CHX)(OHIPT)Cl(Bipy)配合物，该类配合物可被分离并完成结构表征。Mo(N-叔丁基)(亚叔丁基)(OHMT)Cl(PPh2Me)配合物（其中OHMT为O-2,6-(2,4,6-三甲基苯基)苯基，分子式为O-2,6-(2,4,6-Me3C6H2)2C6H3）与(Z)-二氯乙烯[(Z)-ClCH=CHCl]在2,2'-联吡啶存在下反应，得到包含Mo(N-叔丁基)(CHCl)(OHMT)Cl(PPh2Me)与Mo(N-叔丁基)(CHCl)(OHMT)Cl(Bipy)的混合物；但从氘代甲苯(toluene-d8)中结晶析出的相对难溶产物为[Mo(N-叔丁基)(CHPPh2Me)(OHMT)Cl(Bipy)]Cl，即膦𬭩亚甲基配合物。经实验证实，X为Cl、CF3时的Mo(N-叔丁基)(CHX)(OHIPT)Cl(PPh2Me)配合物，可引发(Z)-5-癸烯与(Z)-XCH=CHX之间的立体选择性交叉复分解反应。