Dimerization of Formic Acid-An Example of a “Noncovalent” Reaction Mechanism

The pulse deposition technique allows selectively the isolation of monomeric or dimeric formic acid in argon matrices at 7 K. Warming of matrices containing the monomer M from 7 K to 40 K results in the decrease of M and formation of a dimer B. This dimer is also labile, and further warming finally produces a second dimer A. By comparison with density functional theory (DFT) calculations and gas phase IR spectra taken from the literature, the latter dimer A was identified as the C2h-symmetrical cyclic dimer. The unstable dimer B was identified as the acyclic Cs-symmetrical dimer. An activation energy of 2.3 kcal mol(-1) was calculated for the B --> A rearrangement at the B3LYP/ 6-311 ++ G(d,p) level of theory, which is in qualitative agreement with the experimental finding of a slow thermal reaction under the conditions of matrix isolation.