Authors
Milan Maji, Logan Trowbridge, Maxime Boudjelel, Richard R Schrock, Matthew P Conley, Veronica Carta
Published in
Journal of the American Chemical Society. Jul 08, 2025. Epub Jul 08, 2025.
Abstract
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.
PMID:
40627737
Bibliographic data and abstract were imported from PubMed on 09 Jul 2025.
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