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Synthesis of High-Oxidation-State Mo═CHX Complexes, Where X = Cl, CF3, Phosphonium, CN
Organometallics ( IF 2.5 ) Pub Date : 2018-05-21 , DOI: 10.1021/acs.organomet.8b00168
Sudarsan VenkatRamami 1 , Richard R Schrock 1 , Amir Hoveyda 2 , Peter Müller 1 , Charlene Tsay 1
Affiliation  

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.

中文翻译:

X = Cl,CF 3,Ph,CN的高氧化态Mo═CHX配合物的合成

Z)-XCH = CHX之间的反应,其中X = Cl,CF 3,CN和Mo(N- t- Bu)(CH- t- Bu)(OHIPT)Cl(PPh 2 Me)(OHIPT = O- 2,6-(2,4,6 - i -Pr 3 C 6 H 22 C 6 H 3)生成Mo(N- t -Bu)(CHX)(OHIPT)Cl(PPh 2 Me)络合物。添加2,2'-联吡啶(Bipy)可以生成Mo(N- t- Bu)(CHX)(OHIPT)Cl(Bipy)复合物,可以对其进行分离和结构表征。Mo(N- t- Bu)(CH- t- Bu)(OHMT)Cl(PPh 2)之间的反应Me)(OHMT = O-2,6-(2,4,6-Me 3 C 6 H 22 C 6 H 3)和(Z)-ClCH = CHCl在Bipy存在下产生的混合物包含Mo(N- t- Bu)(CHCl)(OHMT)Cl(PPh 2 Me)和Mo(N- t- Bu)(CHCl)(OHMT)Cl(Bipy),但相对不溶的产物从甲苯- d 8是膦酰基亚甲基络合物[Mo(N- t- Bu)(CHPPh 2 Me)(OHMT)Cl(Bipy)] Cl。Mo(N- t- Bu)(CHX)(OHIPT)Cl(PPh 2 Me)配合物(X = Cl,CF 3)被证实可引发(Z)-5-癸烯与(Z)-XCH = CHX之间的立体选择性交叉复分解。
更新日期:2018-05-22
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