Reaction of titanocene alkyls with pyridines; a novel type of cyclometallation reaction

Imines in the Titanium Coordination Sphere: Highly Reactive Titanaaziridines and Larger Titanacycles Formed by Subsequent C–C Coupling Reactions

“…often characterized by ligand exchange [27,35] as well as insertion reactions. [1,10,[18][19][20][21][22][23]36] In such a way, the titanoceneaziridine 5 undergoes insertion with carbonyl derivatives, whereas insertion reactions with olefins, acetylenes, nitriles, ketones, and aldehydes are found for the (methyleneaniline)titanium complex 6.…”

Catalytic Dearomatization of N‐Heteroarenes with Silicon and Boron Compounds

“…[20] As ac atalytic off-cycle, 1b may undergo reversible dehydrogenative orthometalation to afford the Ti-pyridyl species 1c. [21] Intramolecular C = Ninsertion into the Ti À Hbond of 1bwould take place to give aT i-amido species 1d,w hich then undergoes s-bond metathesis with silane to form ac oordinatively unsaturated hydride complex 1e [22] with release of the N-silyl-1,2-dihydropyridine.Species 1e would rapidly coordinate to pyridine to regenerate 1b.T he released dihydropyridine products can be further hydrogenated to the corresponding tetrahydropyridines.…”

Titanium Hydride Formation through Hydrogen Transfer from 2‐Methylpyridine to a Titanium Fulvene Compound; the First Structurally Characterized Terminal Titanium Hydride

“…Compound 3 was isolated as a dark brown, analytically pure crystalline material; it reacts with D 2 to form EtD and [D]-2 in a 1 :1 molar ratio. [11] The formation of a Ti-H bond through hydrogen transfer from 2-methylpyridine is completely different from what is regularly observed in reactions with compounds of early transition metals of the type [Cp 2 TiR] [12] or [Cp* 2 MR] (M = Sc, [13] Y, [14] Lu [15] ). In the case of a "tucked-in" bonding mode, metalation of the pyridine with hydrogen transfer to the fulvene ligand and formation of [Cp* 2 Ti(η 2 -C 5 H 3 MeN)] is expected.…”