Phosphaniminato-Komplexe des Titans. Synthese und Kristallstrukturen von CpTiCl2(NPMe3), [TiCl3(NPMe3)]2, [Ti2Cl5(NPMe2Ph)3] und [Ti3Cl6(NPMe3)5][BPh4] |
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Authors: | T Rübenstahl F Weller K Harms K Dehnicke D Fenske G Baum |
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Abstract: | Phosphoraneiminato Complexes of Titanium. Synthesis and Crystal Structures of CpTiCl2(NPMe3), TiCl3(NPMe3)]2, Ti2Cl5(NPMe2Ph)3], and Ti3Cl6(NPMe3)5]BPh4] The title compounds are formed from Cp2TiCl2 and titanium tetrachloride, respectively, and the corresponding phosphane imino compounds Me3SiNPMe3 and Me3SiNPMe2Ph. The tetraphenyl borate salt yielded from the reaction of Ti3Cl6(NPMe3)5]Cl with NaBPh4. All compounds form yellow crystals which are sensitive to moisture. They were characterized by IR-spectroscopy and crystal structure analyses. CpTiCl2(NPMe3) ( 1 ): Space group Pbca, Z = 8, solution of the structure with 1632 observed independent reflections, R = 0.037. Lattice dimensions at 19°C: a = 1202.6, b = 1224.2, c = 1766.7 pm. The molecules of the compound are monomeric with the (NPMe3)? ligand in almost linear array (bond angle Ti? N? P 170.7°). TiCl3(NPMe3)]2 ( 2 ): Space group Pbca, Z = 8, structure solution with 698 observed independent reflections, R = 0.030. Lattice dimensions at ?60°C: a = 1140.5, b = 1112.2, c = 1589.4 pm. In 2 the titanium atoms, which occur in trigonal bipyramidal coordination, are linked by the N atoms of the (NPMe3)? groups to form a centrosymmetric dimer with Ti? N bond lengths of 184.3 and 208.2 pm. Ti2Cl5(NPMe2Ph)3] · CH2Cl2 ( 3 ): Space group Pca21, Z = 4, structure solution with 8477 observed independent reflections, R = 0.051. The lattice dimensions at 20°C are: a = 1221.0; b = 1407.5, c = 2139.3 pm. 3 can be understood as a reaction product of TiCl2(NPMe2Ph)2 and TiCl3(NPMe2Ph). In the resulting, heavily distorted Ti2N2-four-membered ring the Ti? N bond lenghts are 1804., 194.4, 199.2, and 234.6 pm. The longest Ti? N bond is in trans-position to the N atom of the terminal (NPMe2Ph)- ligand, in which the Ti? N distance is 175.6 pm. .Ti3CL6(NPMe3)5]BPh4] (4): Space group P21/n, structure solution with 2846 observed independent reflections, R = 0.062. The lattice dimensions at 20°C are: a = 1495.2, b = 2335.4, c = 155,8 pm, β = 93.28°. In the cation of 4 the three titanium atoms along with three (NPMe3)- groups with μ2- N functions and two (NPMe3)- groups with μ3- N functions form a nation number 6 with two terminal chlorine atoms. |
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Keywords: | Phosphoraneiminato Complexes of Titanium Synthesis IR Spectra Crystal Structures |
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