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The unimolecular gas phase chemistry of the title ion,(CH 3 O) 2 P(H)=O  • + , ( 1   • + ) and its tautomer dimethyl phosphite, (CH 3 O) 2 P-OH  • + , ( 2   • + ) was investigated using mass spectrometry based experiments in conjunction with computational quantum chemistry. A facile tautomerization of the "keto" ion  1   • +  into its "enol" isomer  2   • +  is prevented by a high 1,2-H shift barrier. Instead,  1   • +  readily isomerizes via a 1,4-H shift to the very stable distonic ion CH 2 O-(CH 3 O)P(H)OH  • +  ( 1a   • + ) and related ion-dipole complexes which serve as precursors for the low energy loss of CH 2 =O. Loss of CH 2 =O is also the major dissociation of the enol ion  2   • + , which is more stable than  1   • +  by 31 kcal/mol. The reaction involves a 1,3-H shift leading to  1a   • +  and, at a marginally higher energy, a competing 1,4-H shift leading to the ion-dipole complex CH 2 O-P(OH)-O(H)CH 3   • +  ( 1b   • + ). The resulting product ions, viz (CH 3 O)P(H)OH  • +  and P(OH)-O(H)CH 3   • + , are separated by a high 1,2-H shift barrier (44 kcal/mol). However, the CH 2 O moiety in  1a   • +  and  1b   • +  is calculated to reduce this barrier significantly by a mechanism coined as proton-transport catalysis.

Tautomerization and Dissociation of Dimethyl Phosphonate Ions(CH 3 O) 2 P(H)=O • + :Theory and Experiment in Concert