High-field 31P NMR spectroscopy and single crystal X-ray diffraction studies have been used to study the ring opening and nucleophilic substitution reactions of the λ3-cyclotriphosphazane [EtNPCl]3. The synthesis of the ring opened silicophosphonate [RSi(OH){OP(O)(H)(OH)}]2O (R = (2,6-iPr2C6H3)NSiMe3) (1) represents the first ever molecular silicophosphonate to be isolated bearing free reactive hydroxyl groups. The structure and conformation of the bulky aryloxide substituted λ3-cyclotriphosphazane derivative [EtNP(OAr)]3 (Ar = 2,6-iPr2C6H3) (2) has also been investigated. Interaction of 2 with transition metal precursor complexes leads to the isolation of phosphazane metal complexes with different mode of co-ordination of 2. Further, the reaction of Cp *Ti(OAr)Cl2 (Ar = 2,6-(CH3)2C6H3OH) with O[SiPh2(OH)]2 gave the eight-membered trititanosiloxane [Cp*Ti(Cl) {O(SiPh2O)2SiPh2O} (3). Siloxane chain expansion effects, presumed to be a consequence of ring strain, have beer observed in the product. The presence of reactive Ti-Cl bond in 3 offers opportunities for its reaction chemistry to be explored.