Hydration of monomeric metaphosphate anion in the gas phase

Quantum mechanical calculations on phosphate hydrolysis reactions

“…The reverse reactions of 3 and 6 have been widely studied, both experimentally and theoretically as a hydration of metaphosphate problem. Keese and Castleman10 (KC) measured the standard enthalpy, entropy and free‐energy changes for the addition of water to the metaphosphate in gas phase. …”

“…Henchman et al9 found that Rxn 2b did not occur in the gas phase. Keesee and Castleman,10 however, employing more flexible reactions conditions, were able to observe the transition from metaphosphate to orthophosphate.…”

Large amplitude motion in cold monohydrated dihydrogen phosphate anions H2PO4−(H2O): infrared photodissociation spectroscopy combined with ab initio molecular dynamics simulations

“…Early studies on the PO 3 À + H 2 O reaction in the gas phase 4 found that metaphosphate is unreactive, even though H 2 PO 4 À is thermodynamically more stable, owing to a high activation barrier. High pressure mass spectroscopic investigations by Keesee and Castleman, 5 supported by electronic structure calculations, 6,7 suggested that formation of dihydrogen phosphate does occur in the third hydration step and that PO 3 water in a double donor (DD) configuration bound to the two unprotonated phosphoryl O-atoms. 7,[11][12][13] An alternative arrangement with the water in an acceptor-donor (AD) motif is found to be higher in energy.…”

“…Early studies on the PO 3 À + H 2 O reaction in the gas phase 4 found that metaphosphate is unreactive, even though H 2 PO 4 À is thermodynamically more stable, owing to a high activation barrier. High pressure mass spectroscopic investigations by Keesee and Castleman, 5 supported by electronic structure calculations, 6,7 suggested that formation of dihydrogen phosphate does occur in the third hydration step and that PO 3…”

Monoselenophosphate: Its Hydrolysis and Its Ability to Phosphorylate Alcohols and Amines

“…Nevertheless, monomeric metaphosphate is apparently too reactive to have an appreciable lifetime in water to be considered an intermediate although this may not be the case with monomeric thiometaphosphate (32)(33)(34). Interestingly, monomeric metaphosphate appears to be relatively unreactive in the gas phase (35,36). On exposure to water in the gas phase, monomeric metaphosphate forms stable clusters before reacting to form P i .…”