Phosphaniminato-Komplexe von Titan(IV). Die Kristallstrukturen von [TiCl3(NPEt3)]2, [TiCl3(NPEt3)(THF)2] und [TiCl4{Me2Si(NPEt3)2}] |
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Authors: | M M Stahl N Faza W Massa K Dehnicke |
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Abstract: | Phosphoraneiminato Complexes of Titanium(IV). Crystal Structures of TiCl3(NPEt3)]2, TiCl3(NPEt3)(THF)2], and TiCl4{Me2Si(NPEt3)2}] TiCl3(NPEt3)]2 ( 1 ) is formed from titanium(IV) chloride and the silylated phosphaneimine Me3SiNPEt3 in dichloromethane as reddish-brown, moisture-sensitive crystals. According to the crystal structure analysis these crystals show centrosymmetric Ti2N2 four-membered rings with Ti–N distances of 184.7 and 210.3 pm. With tetrahydrofurane 1 forms yellow, moisture sensitive crystals of the solvate TiCl3(NPEt3)(THF)2] ( 2 ), in which the titanium atom is octahedrally coordinated. The THF molecule which is in trans position to the phosporaneiminato ligand realizes but a very weak Ti–O bond of 238.0 pm, the cis THF molecule shows a Ti–O distance of 213.7 pm. With 173.4 pm along with a TiNP bond angle of 160.0° the TiN distance is very short. The bis(phosphaneimine) complex TiCl4{Me2Si(NPEt3)2}] ( 3 ) is formed as colourless crystals in low yield in the reaction of titanium(IV) chloride with Me3SiNPEt3 and trimethylcyclopentadienylsilane. In 3 the titanium atom is surrounded by four chlorine atoms in a distorted octahedral fashion and by the two N atoms of the Me2Si(NPEt3)2 molecule with TiN distances of 205.6 pm. |
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Keywords: | Titanium Compounds Phosphorane Iminato Complexes |
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