Titanium tetramercaptides and dialkylaminotitanium(IV) mercaptides

Abstract

Reactions of excess of thiol R′SH (R′= Me, Et, or Prⁱ) with titanium dialkylamides Ti(NR₂)₄(R = Me or Et) gave insoluble non-volatile red titanium tetramercaptides containing strongly addended thiol and amine, viz., Ti(SR′)₄, (R′SH)_x(R₂NH)_y. It is suggested that these compounds are polymeric owing to mercaptide bridges and that octaco-ordinated titanium may be involved. Controlled addition of ethanethiol or 1-methylethanethiol to Ti(NR₂)₄ gave soluble compounds: Ti(NMe₂)₃SEt, Ti(NMe₂)₂(SEt)₂, Ti(NMe₂)₃SPrⁱ, and Ti(NMe₂)₂(SPrⁱ)₂ which were shown by cryoscopic measurements to be polymeric. Infrared and n.m.r. spectra were also obttained. Reactions with other thiols gave products which could not be characterised.