Über Cyanatverbindungen und deren reaktives Verhalten. XXXI [1]. Solvatfreies Titan(IV)‐thiocyanat und einige abgeleitete Tetrathiocyanato‐bis(ligand)‐titan(IV)‐Komplexe

Abstract

Reaktionen von TiCl4 sowie [TiCla(NCS)bL2]‐Verbindungen führen in Tetrahydrofuran bzw. Acetonitril mit Alkalithiocyanaten zu monomeren Tetrathiocyanato‐bis(ligand)‐titan(IV)‐Komplexen (a = 1, 2, 3; b = 3, 2, 1; L = CH3CN, C4H8O), die mit NH4Cl NH4[TiCl(NCS)4(THF)] · 2 THF bilden. Desolvatation von [Ti(NCS)4(THF)2] führt zu [Ti(NCS)4]x. Die dargestellten Verbindungen werden durch IR‐ und Elektronenspektren sowie Leitfähigkeitsmessungen näher charakterisiert.

Inorganic Metal Thiocyanates

“…Moving right along the periodic table, Ti­(NCS) 4 has been reported to be synthesized by the desolvation of THF solvates at 150 °C under vacuum, producing a red-black crystalline powder. Analysis of the IR spectrum of Ti­(NCS) 4 suggests octahedrally coordinated Ti cations with at least some bridging NCS – anions . These data thus suggest that the structure might be more similar to TiF 4 , a 1D structure comprising corner-sharing TiF 6 octahedra, than the later halides TiX 4 , X = Cl, Br, and I, which are all tetrahedral molecular materials with no Ti–X–Ti bridges. − There are no reports of Zr­(NCS) 4 or Hf­(NCS) 4 , though the DMF solvates of both are reported .…”