Synthesis and Structure of the First Non‐Metallocene Ti^III Fluoride Complex LTiF₂·2Me₃SnCl Supported by a β‐Diketiminato Ligand

Abstract

The TiIII dichloride complex LTiCl2 (1) and the first non‐metallocene TiIII fluoride complex LTiF2·2Me3SnCl (2) supported by the β‐diketiminato ligand 2‐{[2‐(diethylamino)ethyl]amino}‐4‐{[2‐(diethylamino)ethyl]imino}pent‐2‐ene have been synthesized. Elemental analysis, mass spectrometry and X‐ray structural analysis show that 1 is monomeric, neutral, and free of solvent and lithium salt. The complex adopts a pseudo‐octahedral geometry with the two chlorine atoms arranged in trans position to each other. Compound 1 is soluble in common organic solvents and thermally surprisingly robust. Complex 2 was prepared using Me3SnF as a fluorinating agent. X‐ray structural analysis revealed that complex 2 consists of the LTiF2 unit and two molecules of Me3SnCl coordinated through a fluorine bridge to the titanium center. The fluorine atoms in 2 are located in trans positions to each other and the geometry around the titanium atom is distorted octahedral. Elemental analysis and mass spectrometry proved that 2 releases the coordinated Me3SnCl under vacuum or during sublimation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Vanadium complexes incorporating the β-diketiminato ligand L. Syntheses and structures of LV(OSO2CF3)2and LVPPh2

“…Previously we have reported the synthesis and structural characterization of new derivatives of titanium LTiX 2 (L = N,NЈ-bis(2-diethylaminoethyl)-2,4pentanediimineate(1Ϫ), X = Cl, FؒSnMe 3 Cl), belonging to a novel class of metal complexes containing a β-diketiminatobased ligand which possesses two dangling arms. 4 Herein we report the synthesis of LVCl 2 and subsequent reactions with different nucleophiles, other than alkyls, that were carried out. The structure of LV(OSO 2 CF 3 ) 2 , which represents the first vanadium() triflate derivative structurally characterized, and the structure of LVPPh 2 which represents the first neutral heteroleptic terminal diorganophosphido complex of vanadium(), are also described.…”

Cyclopentadienyl Free Compounds of p, d, and f Elements

“…Accordingly, some complexes of titanium [61] and vanadium with the L ligand system have been prepared. Even though the structure of the LVCl 2 , 17, could not be determined yet, in order to get the final proof about its constitution, the metathesis reaction with The bonding mode of the ligand L in the vanadium complexes is similar to that found in the lanthanide complexes.…”

“…The chemistry of the early transition metals, especially the chemistry of scandium with L has increased to a great extent, as a result unusual C-H bond activation [47a] and oxidation state being accomplished. [23] Besides, L containing complexes of the following electrophilic metals as titanium, [61] yttrium, [48] lanthanum, [48] cerium, [48] holmium, [48] erbium, [48] and lutetium [48] have been prepared and characterized. New insights about the polydentate behaviour of the ligand L have been Results and Discussion revealed when complexes with aluminum and vanadium were prepared.…”