Syntheses and Properties of Cyclopentadienyl-Substituted Imidotitanium Fluorides

Abstract

The reaction of 2 equiv of Me3SnF with [(η5-C5H4Me)TiCl(NPh)]2 in the presence of at least 2 equiv of pyridine affords [(η5-C5H4Me)TiF(NPh)]2 (1) in high yield. (η5-C5H4SiMe3)TiCl(N-t-Bu)·py reacts quantitatively with an equimolar amount of Me3SnF to yield [(η5-C5H4SiMe3)TiF(N-t-Bu)]2 (2). The fluorides [η5-Cp‘TiF(NSnMe3)]2 (Cp‘ = C5Me4Et (3), C5H4Me (4)) are obtained in high yield by reaction of N(SnMe3)3 with (η5-C5Me4Et)TiF3 and (η5-C5H4Me)TiF3, respectively. Complex 3 has been characterized by X-ray diffraction. (MeAlNMes)4 (Mes = 2,4,6-trimethylphenyl) reacts as a transamination reagent with 4 equiv of (η5-C5H4Me)2TiF2 to provide [(η5-C5H4Me)TiF(NMes)]2 (5) in low yield.

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

“…The insolubility of trimethyltin fluoride, in combination with the high volatility and solubility of trimethyltin chloride makes this an "ideal fluorinating system". 16 Halide metathesis proceeds equally well in the presence of oxygen- 16,18,19 and nitrogen 20 -containing ligands. In addition trimethyltin fluoride has proven effective in the fluorination of transition metal hydride 21 and alkyl derivatives.…”

Synthesis and Reductive N−N Bond Cleavage of Neutral and Cationic Titanium (1-Pyridinio)imido Complexes

“…Complexes 3a − c contain a titanium center coordinated by one Cp (or Cp*), two chlorine atoms, and one imido nitrogen atom, making the complexes monomeric. In contrast, monocyclopentadienyl titanium imido complexes with just one halogen atom have a dimeric structure [(Cp‘TiX) 2 (μ-NR) 2 ] (X = F, Cl; R = alkyl, aryl) in the absence of added ligand . Complexes 3a − c rather resemble imido complexes of the type Cp‘MCl 2 (N−R) (Cp‘ = Cp, Cp*; R = alkyl, aryl) having four-electron-donor imido ligands (taking the imido ligand as a neutral ligand for electron-counting) and group 5, 6, and 7 metal centers: Nb and Ta, Mo and W, and Re .…”

Neue Methoden zur Fluorierung von Verbindungen früher Übergangsmetalle

“…Reduktionen von perfluorierten Kohlenwasserstoffen [10], Transaminierungen von organometallischen Fluoriden der 4. Gruppe [11], Synthese von Verbindungen mit Hauptgruppen-Übergangsmetallbindungen [12,13], intramolekulare C-F-Bindungsaktivierung [14,15], C-H-Bindungsaktivierung [16],…”

“…Die Fluorierung kann durch Metathese der entsprechenden Chlorokomplexe mit Hilfe von ionischen Fluoridquellen wie NaF oder AgF geschehen. Aufgrund von Komplexierungen des entstehenden Organometallfluorids durch freies Fluorid läßt sich das gewünschte Produkt nicht rein oder nur in geringer Ausbeute isolieren [26 -28] Sauerstoff [21,30,31] und Stickstoff [11] enthaltende Liganden werden von Me 3 SnF toleriert. Weitere Synthesewege werden durch Metathese von Metallhydriden [32] und Alkylderivaten [33,34] [45], (BisGe) 6 [46], (BisSb) 3 [47] und (BisBi) 4 [48], deren Kristallstrukturen bestimmt werden…”