Since the initial report of Tebbe reagent in 1978, group 4 methylidene chemistry and its reactivity studies have been extensively reported. Schwartz and Gell reported the synthesis of the mononuclear zirconium methylidene Cp2Zr(=CH2)(PPh2Me) in 1980, but its instability limited the reactivity study to only a protonation by HOtBu or with electrophiles like MeI. In 1989, Grubbs recognized the titanium methylidene Cp2Ti(=CH2)(PR3) (PR3 = PMe3, PEt3, PMe2Ph) to be stable at -40 °C and reported reactivity studies with unsaturated reagents (CO, olefins and alkynes). We recently reported the first example of a structurally characterized zirconium terminal methylidene complex [(PNP)Zr(=CH2)(OAr)] with a hindered set of ligand scaffolds, PNP and OAr (PNP– = [N-(2-diisopropylphosphino-4-methylphenyl)2]–, ArO– = 2,6-diisopropyl-phenoxide). In this study we will report reactivity studies of this kinetically stable zirconium methylidene such as methylidene group transfer, methylenations, and C–H activation. This presentation will also discuss an unusual N–N bond activation of 1-azidoadamantane by [(PNP)Zr(CH2)(OAr)] to form a parent ketimide complex.

Group transfer and methylenation reactions of a terminally bound zirconium methylidene complex

253rd National Meeting (2017)

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