Darstellung und Struktur neuer Calix[4]aren-Titan(IV)-Imidokomplexe
Abstract
deAusgehend von [Cax(OMe)2O2TiCl2] (1) und den Lithiumamiden LiNHtBu und LiNHMes (Mes = 2,4,6-Trimethylphenyl) lassen sich die Calix[4]aren-Titan(IV)imidokomplexe [Cax(OMe)2O2Ti(NR)] (2) (R = tBu) und (3) (R = Mes) (Cax = C44H52) in guten Ausbeuten darstellen. Bei diesen Verbindungen handelt es sich um in Lösung monomere Komplexe. Von 3 · C7H8 konnte eine Röntgenstrukturanalyse angefertigt werden. Raumgruppe: P 1, Gitterkonstanten: a = 12.979(2) Å, b = 13.707(2) Å, c = 16.573(3) Å, α = 81.751(11)°, β = 80.555(13)°, γ = 73.541(12)°. Das Zentralatom in 3 ist annähernd trigonal bipyramidal koordiniert, der Titan–Stickstoff Bindungsabstand zur nahezu linearen Imidoeinheit beträgt 171.8(3) pm.
Abstract
enSynthesis and Structure of New Calix[4]arene Titanium(IV) Imido Complexes
The syntheses of the novel calix[4]arene titanium imido compounds [Cax(OMe)2O2Ti(NR)] (2) (R = tBu) and (3) (R = Mes = 2,4,6-trimethylphenyl) (Cax = C44H52) starting from [Cax(OMe)2O2TiCl2] (1) and lithium amides LiNHR are described. Complexes 2 and 3 are mononuclear compounds in solution. An X-ray crystal structure analysis of the toluene adduct of 3 (Space group: P 1, lattice dimensions: a = 12.979(2) Å, b = 13.707(2) Å, c = 16.573(3) Å, α = 81.751(11)°, β = 80.555(13)°, γ = 73.541(12)°) reveals that this compound is mononuclear in the solid state. The central atom in 3 is distorted trigonal bipyramidal ligated by two ether oxygen atoms in axial positions, two phenoxide oxygen atoms in the equatorial plane, and an imido nitrogen atom in an equatorial position. The titanium nitrogen bond distance in 3 is 171.8(3) pm.
