Ring Contraction of a Tungstacyclopentane Supported on Silica: Direct Conversion of Ethylene to Propylene
Ring Contraction of a Tungstacyclopentane Supported on Silica: Direct Conversion of Ethylene to Propylene
复制标题
二氧化硅负载的钨环戊烷的环收缩：乙烯直接转化为丙烯
DOI：
10.1021/jacs.2c07934
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发表时间：
2022
影响因子：
15
通讯作者：
Conley, Matthew P.
中科院分区：
文献类型：
--
作者：
Rodriguez, Jessica;Boudjelel, Maxime;Mueller, Leonard J.;Schrock, Richard R.;Conley, Matthew P.
W(NaR)(13C4H8)(OSiPh3)2(1)(NaR=2，6-二异丙基苯亚胺)与700℃(SiO_2-700)部分脱羟基的二氧化硅的反应与反应条件密切相关。该反应在黑暗中进行，主要产物为W(NaR)(13C4H8)(OSiPh3)(OSi(O−)3)(2)。在实验室条件下，将1接枝到W(NAr)(13CH213CH(13Me)13CH2)(OSiPh3)(OSi(O−)3)-700分子筛上，生成2，W(NaR)(13CH213CH2)(OSiPh3)(OSi(O−)3)(4)和一个四方锥体OSiPh异构体(3)。2℃至85℃加热6h，生成3，4，W(NAr)(13CH(13Me)13CH213CH2)(OSiPh3)(OSi(O−)3)(5)和W(NAr)((13CH2)213CH(13Me)(13CH2)2)(OSiPh3)(OSi(O−)3)(6)。2用蓝色发光二极管(λmax=450 nm)光解产生4，3，5和游离乙烯的两种异构体。在过量乙烯和85°C蓝光LED照射下，1/SiO_2-700催化乙烯直接转化为丙烯。
The reaction of W(NAr)(13C4H8)(OSiPh3)2(1) (NAr = 2,6-diisopropylphenylimido) with silica partially dehydroxylated at 700 °C (SiO2-700) is highly dependent on the reaction conditions. The primary product of this reaction is W(NAr)(13C4H8)(OSiPh3)(OSi(O−)3) (2) when the reaction is carried out in the dark. Grafting1onto SiO2-700in ambient lab light results in the formation of2, W(NAr)(13CH213CH2)(OSiPh3)(OSi(O−)3) (4), and one isomer of square-pyramidal W(NAr)(13CH213CH(13Me)13CH2)(OSiPh3)(OSi(O−)3) (3). Heating2to 85 °C for 6 h results in the formation of3,4, W(NAr)(13CH(13Me)13CH213CH2)(OSiPh3)(OSi(O−)3) (5), and W(NAr)((13CH2)213CH(13Me)(13CH2)2)(OSiPh3)(OSi(O−)3) (6). Photolysis of2with blue LEDs (λmax= 450 nm) produces 4, both isomers of 3,5, and free ethylene. In the presence of excess ethylene and blue LED irradiation at 85 °C,1/SiO2-700catalyzes the direct conversion of ethylene to propylene.