The monoazidotitanium trisisopropoxide {(N-3)Ti(OiPr)(3)}(4) (2) was obtained by the reaction of (N-3)(2 center dot)Ti(OiPr)(2) (1) with Ti(OiPr)(4). Colorless 2 possesses an interesting tetrameric structure featuring bridging azide and isoproxide ligands and five- and six-coordinate titanium centers. It can be sublimed in vacuo at ca. 130 degrees C but decomposes rapidly above 180 degrees C. Controlled hydrolysis afforded the related yellow oxo cluster (iPrO)(8)Ti-4(mu-OiPr)(2)(mu(4)-O)(mu-N-3)(4) (3).