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Proton-Catalyzed Interconversion of Tungsten(VI) Imido Isopropylidene and Propylene Complexes
Milan Maji1, Logan Trowbridge1, Maxime Boudjelel1
1Department of Chemistry, University of California at Riverside, Riverside, California 92521, United States.
None:
Additions of two equivalents of (CF3)3COH (RF9OH) or (CF3)2MeCOH (RF6OH) to W(NAr)2R2 complexes (Ar = 2,6-diisopropylphenyl, R = n-propyl or i-propyl) offer the opportunity to synthesize propylene or isopropylidene olefin metathesis-active complexes in the absence of free propylene. Propylene and isopropylidene complexes (W(NAr)(ArNH2)(ORF9)2(propylene) and W(NAr)(ArNH2)(ORF9)2(CMe2)) are formed at room temperature from both W(NAr)2(i-propyl)2 and W(NAr)2(n-propyl)2 complexes upon addition of two equivalents of RF9OH; no W = CHCH2Me complexes are observed. Similar results are found for W(NAd)2(propyl)2 complexes (Ad = 1-adamantyl). Both RNH2 and RNH2B(C6F5)3 (R = Ar or Ad) catalyze the interconversion of propylene and isopropylidene complexes. Addition of RF6OH to W(NAr)2R2 or W(NAd)2R2 complexes leads to mixtures that contain largely propylene complexes. Addition of (CF3)Me2COH (RF3OH) to W(NAr)2(i-Pr)2 yields only propylene complexes. One propylene complex, W(NAd)(ORF9)2(CH2═CHMe)(dme), was isolated, structurally characterized, and found to react with AdNH2 to reform W(NAd)(ORF9)2(CMe2)(AdNH2). It is proposed that propylene and isopropylidene complexes interconvert through the formation of an intermediate isopropyl complex.
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