Syntheses of Molybdenum Adamantylimido and t-Butylimido Alkylidene Chloride Complexes Using HCI and Diphenylnnethylphosphine
Syntheses of Molybdenum Adamantylimido and t-Butylimido Alkylidene Chloride Complexes Using HCI and Diphenylnnethylphosphine
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DOI：
10.1021/acs.organomet.7b00647
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发表时间：
2017-11-13
期刊：
影响因子：
2.8
通讯作者：
Schrock, Richard R.
中科院分区：
文献类型：
--
作者：
Bukhryakov, Konstantin V.;VenkatRamani, Sudarsan;Schrock, Richard R.
Mo（N-t-Bu）（2）（CH_2-t-Bu）（2）或Mo（N-金刚烷基）（2）（CH_2CMe_2 Ph）（2）与3当量HCl在1当量PPh_2Me存在下反应，生成Mo（NR）（CHR ′）（PPh_2Me）Cl ~-_2配合物，由此可制备Mo（NR）（CHR ′）（PPh_2Me）（OAr）Cl配合物（OAr = 2，6-三苯氧基）。研究了Mo（NR）（CHR '）（PPh_2Me）（OAr）Cl配合物作为环辛烯与Z-1，2-二氯乙烯交叉复分解反应催化剂的性能。当OAr为OHMT或OHIPT时，OAr = OTPP、OHMT、OHIPT或OHTBT（其中OTPP为2，3，5，6-四苯基苯酚盐，OHMT为六甲基三苯醚，OHIPT为六异丙基三苯醚，OHTBT为六叔丁基三苯醚）的络合物的测试反应效率最大。Mo（N-t-Bu）（CH-t-Bu）（PPh 2 Me）Cl-2对环辛烯与Z-1，2-二氯乙烯的反应基本上无活性。对Mo（NAd）（CHCMe 2 Ph）（PPh 2 Me）Cl-2、Mo（N-t-Bu）（CH-t-Bu）（PPh 2 Me）（OHMT）Cl、Mo（NAd）（CHCMe 2 Ph）（Cl）（OHTBT）（PMe 3）和Mo（NAd）（CHCMe 2 Ph）（Cl）（OHTBT）（PMe 3）与0.5当量水反应的产物[Mo（NAd）（CHCMe 2 Ph）（PMe 3）（Cl）]（2）（μ-O）进行X射线结构研究。
Reactions between Mo(N-t-Bu)(2)(CH2-t-Bu)(2) or Mo(NAdamantyl)(2)(CH2CMe2Ph)(2) and 3 equiv of HCl in the presence of 1 equiv of PPh2Me yield Mo(NR)(CHR')(PPh2Me)Cl-2 complexes, from which Mo (NR)(CHR')(PPh2Me)(OAr)Clcomplexes (OAr = a 2,6-terphenoxide) can be prepared. The Mo(NR)(CHR')(PPh2Me)(OAr)Cl complexes were evaluated as cross-metathesis catalysts between cyclooctene and Z-1,2-dichloroethylene. The efficiencies of the test reaction for complexes in which OAr = OTPP, OHMT, OHIPT, or OHTBT (where OTPP is 2,3,5,6-tetraphenylphenoxide, OHMT is hexamethylterphenoxide, OHIPT is hexaisopropylterphenoxide, and OHTBT is hexa-t-butylterphenoxide) maximize when OAr is OHMT or OHIPT. Mo(N-t-Bu)(CH-t-Bu)(PPh2Me)Cl-2 is essentially inactive for the reaction between cyclooctene and Z-1,2-dichloroethylene. X-ray structural studies were carried out on Mo(NAd)(CHCMe2Ph)(PPh2Me)Cl-2, Mo(N-t-Bu)(CH-t-Bu)(PPh2Me)(OHMT)Cl, Mo(NAd)(CHCMe2Ph)(Cl)(OHTBT)(PMe3), and [Mo(NAd)(CHCMe2Ph)(PMe3)(Cl)](2)(mu-O), the product of the reaction between Mo(NAd)(CHCMe2Ph)(Cl)(OHTBT)(PMe3) and 0.5 equiv of water.