synthesis and structural characterisation of titanium(IV) thiolate compounds

摘要

Synthetic and structural studies have been performed for two thiolate complexes of titanium(IV). The reaction between Ti(Net_2)_4 and 10 equivalents of C_6F_5SH at room temperature resulted in the formation of the ionic complex [Et_2NH_2]_3[Ti(SC_6F_5)_5][SC_6F_5]_2. The related reaction between Ti(Net_2)_4 and 4 equivalents of C_6F_5SH at room temperature, in the presence of a two electron donor ligand L (2,6-dimethylpyridine or tetrahydrothiophene), resulted in the isolation of the ionic complex [Et_2NH_2][Ti(SC_6F_5)_4(Net_2)]. However, if the reaction between Ti(Net_2)_4 and 4 equivalents of C_6F_5SH is carried out without the addition of L, the first compound is formed rather than the second. The two new complexes have been characterised by X-ray crystallography. [Et_2NH_2]_3[Ti(SC_6F_5)_5][SC_6F_5]_2 is the first structurally characterised example of a five-co-ordinate homoleptic sulfur-bonded titanium complex. Both adopt simlar sheet structures held together by #pi#-#pi# and C-F…#pi# interactions.