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

Abstract

An unusual structure and a unique route of formation characterize the title compound 1. It is formed from the fulvene‐titanium compound [Cp*(C5Me4CH2)Ti] and 2‐methylpyridine in ether. H‐6 of the pyridine derivative migrates to Ti, and the fulvene ligand is transformed by CC bond formation into a functionalized cyclopentadienyl ligand (Cp*=η5Me5).

Vivid Wording for the Chemistry of Group 4 Metallocene Complexes

“…For titanium complexes Teuben et al. described [(C 5 Me 5 ) 2 Ti] as “tuck(ed)‐in” and discussed a double C−H activation to yield the dihydride [(C 5 Me 5 ){C 5 Me 3 (CH 2 ) 2 }TiH 2 ] [3b] . It should be mentioned that Bercaw and co‐workers described such compounds previously as cyclopentadienylmethyl or neutral complexes with conjugated trienes (Scheme 1).…”

Anschauliche Bezeichnungen der Chemie von Metallocen‐Komplexen der Gruppe 4

“…Für Titankomplexe sicherten Teuben et al. dieses für [(C 5 Me 5 ) 2 Ti] als “tuck(ed)‐in” und diskutierten eine doppelte C‐H‐Aktivierung zum Dihydrid [(C 5 Me 5 ){C 5 Me 3 (CH 2 ) 2 }TiH 2 ] [3b] . Es ist zu anzumerken, dass Bercaw und Mitarbeiter vorher solche Verbindungen als Cyclopentadienylmethyl‐ oder Neutralkomplexe konjugierter Triene beschrieben hatten (Schema 1).…”

“…erfolgt [3f,g] . Andere wichtige Untersuchungen von Teuben und Mitarbeitern, [,3b,h–j] zeigten, dass der Tetramethylfulven‐Ti III ‐Komplex [Cp*Ti{C 5 Me 4 (CH 2 )}] [3k] das Intermediat für verschiedenste C‐C‐Kupplungsreaktionen des Decamethyltitanocens, wie z. B. mit Ketonen [3i] und Isocyaniden, ist [3m] .…”

Hydrogen Storage Properties of B₁₂Sc₄ and B₁₂Ti₄ Clusters

“…The calculated Ti-H bond length in TiH4 is about 0.170 nm, 44 and the experimental values range from 0.169 to 0.184 nm in different compounds. 45,46 The H-H distance of B12Ti4-4H2 is 0.079 nm, which is 0.005 nm longer than that of free hydrogen molecule. The ABE/H2 of B12Ti4-4H2 is -67.5 kJ·mol -1 , which is remarkably larger than that of B12Sc4-4H2.…”