Premium
Gaseous H 5 P 2 O 8 − Ions: A Theoretical and Experimental Study on the Hydrolysis and Synthesis of Diphosphate Ion
Author(s) -
Pepi Federico,
Ricci Andreina,
Rosi Marzio,
Di Stefano Marco
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400293
Subject(s) - fourier transform ion cyclotron resonance , chemistry , ion , analytical chemistry (journal) , mass spectrometry , dissociation (chemistry) , electrospray ionization , ionic bonding , ion cyclotron resonance , cyclotron , organic chemistry , chromatography
The structure and reactivity of gaseous H 5 P 2 O 8 − ions obtained from the chemical ionization (CI) of an H 4 P 2 O 7 /H 2 O mixture and from electrospray ionization (ESI) of CH 3 CN/H 2 O/H 4 P 2 O 7 solutions were investigated by Fourier transform ion cyclotron (FTICR) and triple quadrupole mass spectrometry. Theoretical calculations performed at the B3LYP/6‐31+G* level of theory and collisionally activated dissociation (CAD) mass spectrometric results allowed the ionic population obtained in the CI conditions to be structurally characterized as a mixture of gaseous [H 3 P 2 O 7 ⋅⋅⋅H 2 O] − , [H 3 PO 4 ⋅⋅⋅H 2 PO 4 ] − , and [PO 3 ⋅⋅⋅H 3 PO 4 ⋅⋅⋅H 2 O] − clusters. The energy profile emerging from theoretical calculations affords insight into the mechanism of diphosphate ion hydrolysis and synthesis.