高氧化态Mo═CHX配合物的合成，其中X = Cl、CF、鏻、CN。
Synthesis of High-Oxidation-State Mo═CHX Complexes, Where X = Cl, CF, Phosphonium, CN.
作者信息
VenkatRamami Sudarsan, Schrock Richard R, Hoveyda Amir, Müller Peter, Tsay Charlene
机构信息
Department of Chemistry 6-331, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139.
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467.
出版信息
Organometallics. 2018 Jun 11;37(11):1641-1644. doi: 10.1021/acs.organomet.8b00168. Epub 2018 May 21.
Reactions between -XCH=CHX where X = Cl, CF, or CN and Mo(N--Bu)(CH--Bu)(OHIPT)Cl(PPhMe) (OHIPT = O-2,6-(2,4,6--PrCH)CH) produce Mo(N--Bu)(CHX)(OHIPT)Cl(PPhMe) complexes. Addition of 2,2'-bipyridyl (Bipy) yields Mo(N--Bu)(CHX)(OHIPT)Cl(Bipy) complexes, which could be isolated and structurally characterized. The reaction between Mo(N--Bu)(CH--Bu)(OHMT)Cl(PPhMe) (OHMT = O-2,6-(2,4,6-MeCH)CH) and -ClCH=CHCl in the presence of Bipy produces a mixture that contains both Mo(N--Bu)(CHCl)(OHMT)Cl(PPhMe) and Mo(N--Bu)(CHCl)(OHMT)Cl(Bipy), but the relatively insoluble product that crystallizes from toluene- is the phosphoniomethylidene complex, [Mo(N--Bu)(CHPPhMe)(OHMT)(Cl)(Bipy)]Cl. The Mo(N--Bu)(CHX)(OHIPT)Cl(PPhMe) complexes (X = Cl or CF) were confirmed to initiate the stereoselective cross-metathesis between -5-decene and -XCH=CHX.
在X = Cl、CF或CN时，-XCH=CHX与Mo(N--Bu)(CH--Bu)(OHIPT)Cl(PPhMe)（OHIPT = O-2,6-(2,4,6--PrCH)CH）之间的反应生成Mo(N--Bu)(CHX)(OHIPT)Cl(PPhMe)配合物。加入2,2'-联吡啶（Bipy）可生成Mo(N--Bu)(CHX)(OHIPT)Cl(Bipy)配合物，这些配合物可被分离并进行结构表征。在Bipy存在下，Mo(N--Bu)(CH--Bu)(OHMT)Cl(PPhMe)（OHMT = O-2,6-(2,4,6-MeCH)CH）与-ClCH=CHCl反应生成一种混合物，其中包含Mo(N--Bu)(CHCl)(OHMT)Cl(PPhMe)和Mo(N--Bu)(CHCl)(OHMT)Cl(Bipy)，但从甲苯中结晶出来的相对不溶的产物是膦亚甲基配合物[Mo(N--Bu)(CHPPhMe)(OHMT)(Cl)(Bipy)]Cl。已证实Mo(N--Bu)(CHX)(OHIPT)Cl(PPhMe)配合物（X = Cl或CF）可引发-5-癸烯与-XCH=CHX之间的立体选择性交叉复分解反应。
Zotero 插件