Abstract
The positive and negative gas-phase ion chemistry of Ti(O-i-Pr)4 was investigated at low pressures by FT-ICR. The fragment ion, (i-PrO)3Ti-O+=C(H)Me, reacts with the parent neutral by proton transfer and by a nucleophilic additionelimination reaction. The nature of the fragment ion and the ensuing ionmolecule reactions clearly indicate that Ti(O-i-Pr)4 exists as a monomer in the gas phase. In the negative ion mode, F was found to react easily with Ti(O-i-Pr)4 to yield the pentacoordinated complex FTi(O-i-Pr)4 ion. This hypervalent Ti species undergoes a series of sequential fragmentations induced by IR multiphoton excitation. The first step is unusual because two channels are observed by IRMPD: one involves loss of HF, and the other loss of i-PrOH. The subsequent dissociation processes are characterized by progressive elimination of propene giving rise to a number of different titanaoxirane-containing anions with the general formula [(η2-CMe2O)Ti(OH)3n(i-PrO)n]. FTi(O-i-Pr)4 was also observed to undergo multiple alkoxidefluoride exchanges with BF3 leading to the eventual formation of TiF5.Key words: titanium tetraisoproxide, gas-phase ion chemistry, hypervalent Ti, ionmolecule reactions, IRMPD.
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