ArticleAngewandte Chemie (International ed. in English)2026
Bent N-Heterocyclic Allenes From a Well-Defined Titanium Vinylidene Complex.
Article in Angewandte Chemie (International ed. in English), 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Allenes typically display a linear geometry. A notable exception occurs in allenes bearing two electron-donating N-heterocyclic capping groups, which can display a strongly bent C═C═C unit. These push-push allenes, known as carbodicarbenes, are powerful carbon-donor ligands with broad utility in chemistry. Computational studies have suggested that push-pull allenes, featuring both an electron-donating and withdrawing capping group, can also adopt a bent geometry. However, experimental confirmation has so far been lacking. Herein, we report allenes featuring an N-heterocyclic capping group on one side, and either diarylmethylidene or fluorenylidene capping groups on the other. The synthesis of these allenes was accomplished via a titanium vinylidene complex. The latter could be isolated and analyzed by X-ray diffraction, and it represents the first structurally characterized Ti vinylidene complex. The push-pull allenes with fluorenylidene capping groups revealed markedly bent C═C═C units (α
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