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B(C6F5)3 Activation of Oxo Tungsten Complexes That Are Relevant to Olefin Metathesis

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Figshare2016-02-18 更新2026-04-29 收录
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https://figshare.com/articles/dataset/B_C_sub_6_sub_F_sub_5_sub_sub_3_sub_Activation_of_Oxo_Tungsten_Complexes_That_Are_Relevant_to_Olefin_Metathesis/2367100
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We have found that coordination of B­(C6F5)3 to an oxo ligand in tungsten oxo alkylidene bis­(aryloxide) complexes, where the aryloxide is O-2,6-(mesityl)2C6H3 (HMTO) or 2,6-diadamantyl-4-methylphenoxide (dAdPO), accelerates the formation of metallacyclobutane complexes from alkylidenes as well as the rearrangement of metallacyclobutane complexes. In contrast, a tungstacyclopentane complex, W­(O)­(C4H8)­(OHMT)2, is relatively stable toward rearrangement in the presence of B­(C6F5)3. A careful balance of steric factors allows a single isomer of W­(O)­(trans-4,4-dimethylpent-2-ene)­(dAdPO)2 to be formed from W­(O)­(CH-t-Bu)­(dAdPO)2 in the presence of both ethylene and B­(C6F5)3.
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2016-02-18
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