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Creators/Authors contains: "Hernandez, George M"

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  1. ; ; (, Organometallics)
    Early transition metal alkyl and hydride complexes have been widely explored for their propensity to faciltate C–H activation through a concerted σ-bond metathesis mechanism. Herein, we report the synthesis of a tris(amido) Zr(IV) alkyl complex 1 as a precursor of accessing a proposed transient Zr(IV)-hydride. Upon intramolecular C–H activation of a pendent methyl group, a strained cyclometalated complex 2 is obtained. Relief of ring strain and cooperative metal–ligand C–H activation provided access to Zr-acetylide complex 3, which is capable of undergoing insertion reactivity into carbonyl containing compounds, like aldehydes and ketones. Complexes 1–3 are characterized using multinuclear NMR spectroscopy, UV–vis spectroscopy, and X-ray crystallography. Newly reported electron-rich propargylic alcohols 6 and 7 are isolated and fully characterized using multinuclear NMR spectroscopy, ESI-MS, and FTIR. 
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    Free, publicly-accessible full text available August 6, 2026