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

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posted on 18.02.2016, 16:15 by Dmitry V. Peryshkov, William P. Forrest, Richard R. Schrock, Stacey J. Smith, Peter Müller
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.