Reaction of titanocene dichloride [Cp₂TiCl₂] (Cp = C₅H₅) with (^tBuO)₂PO₂H (di-tert-butylphosphate, dtbpH) in THF at room temperature results in the formation of mononuclear titanophosphate [Cp₂Ti(dtbp)₂].H₂O (1), whereas the reaction of potassium salt of dtbpH (dtbpK) with [Cp₂TiCl₂] in THF yields tetranuclear cluster [Cp₄Ti₄(µ-O)₃(µ-dtbp)₂(dtbp)₂(µ-mtbpH)₂].2C₆H₅CH₃ (2) (mtbpH = (^tBuO)PO₃H). Change of the reaction medium to acetonitrile for the reaction dtbpK with [Cp₂TiCl₂] leads to the isolation of novel hexanuclear titanophosphate cluster [Ti₆(µ-O)₆(µ-OH)₃(µ-dtbp)₉] (3), which is free of cyclopentadienyl ligands. Compound 1, when dissolved in CH₃CN and allowed to stand under aerobic conditions, converts to either 2 or 3, depending on the dilution (water content in the medium) and the duration of crystallization. While lesser water content and shorter crystallization periods produce 2 as orange crystals, longer exposure of the solution results in the complete hydrolysis of Cp-Ti linkages and produce colorless, Cp-free hexanuclear cluster 3. In contrary, the reaction of either dtbpH or its potassium salt with zirconocene dichloride exclusively leads to the formation of [CpZr(µ-OH)(µ-dtbp)(dtbp)]₂ (4) as the only product. Compounds 1-4 have been characterized by analytical and spectroscopic methods. Their molecular structures have further been established by single-crystal X-ray diffraction studies. Thermal decomposition of 1 reveals its thermolabile nature with the initial loss of alkyl substituents of the organophosphate ligands through β-hydride elimination followed by the loss of C₅H₅ groups to form an organic-free crystalline titanium phosphate phases which sinter finally to titanium pyrophosphate TiP₂O₇ at 800 ˚C.

室温下二茂钛二氯化物[Cp ₂ TiCl ₂ ]（Cp = C ₅ H ₅）与（^t BuO）₂ PO ₂ H（磷酸二叔丁酯，dtbpH）在THF中的反应导致形成单核钛磷酸盐[Cp ₂ Ti（dtbp）₂ ] .H ₂ O（1），而dtbpH的钾盐（dtbpK）与[Cp ₂ TiCl ₂ ]在THF中的反应生成四核簇[Cp ₄ Ti ₄（µ-O）₃（ µ-dtbp）₂（dtbp）₂（μ-mtbpH）₂ ] .2C ₆ H ₅ CH ₃（2）（mtbpH =（^t BuO）PO ₃ H）。将dtbpK与[Cp ₂ TiCl ₂ ]反应的反应介质更改为乙腈可导致分离出新的六核钛磷酸盐簇[Ti ₆（µ-O）₆（µ-OH）₃（µ-dtbp）₉ ]（3），其不含环戊二烯基配体。化合物1溶于CH ₃ CN并在有氧条件下放置时，会转化为2或3，具体取决于稀释度（介质中的水含量）和结晶时间。较少的水含量和较短的结晶时间会生成2个橙色晶体，而溶液的长时间暴露会导致Cp-Ti键完全水解，并产生无色，不含Cp的六核簇3。相反，dtbpH或其反应钾盐与二氧化锆一起唯一地导致形成[CpZr（µ-OH）（µ-dtbp）（dtbp）] ₂（4）。化合物1-4已经通过分析和光谱方法表征。通过单晶X射线衍射研究进一步确定了它们的分子结构。1的热分解显示了其热不稳定的性质，有机磷配体的烷基取代基最初通过β氢化物消除而失去，然后失去C ₅ H ₅基团形成无有机的结晶磷酸钛相，最终烧结成焦磷酸钛。 TiP ₂ O ₇在800˚C 。