Abstract: | Infrared spectroscopy and matrix isolation technique have been used to study the 1 : 1 complexes formed between 2,4,5-trichlorophenol (TCP), pentachlorophenol (PCP) or 2-chloro-4,6-dinitrophenol (CNP) and trimethylamine (TMA) isolated in solid argon. The results were analyzed in relation to the type of complex formed. Depending on the proton-donor ability of the phenol three different types of hydrogen bonded complexes have been identified in argon matrices. The weakest phenol in the series, TCP (pKa = 6.72), forms a strong molecular hydrogen bonded complex with TMA as indicated by the broad ν(OH N) absorption with a maximum at 2490 cm?1 and a band at 811 cm?1 due to the νs(C3N) mode of the perturbed amine. The strongest phenol, CNP (pKa = 2.01), interacts with TMA in an argon matrix to form ionic complex with the proton transferred to the base molecule. This is evidenced by the presence of the ν(NH+---O?) absorption between 3000?1800 cm?1, by the νas(C3N+) and νs(C3N+) absorptions due to the protonated amine and by numerous product bands due to the relatively strongly perturbed modes of the phenol ring. The interaction between TMA and a phenol of intermediate strength, PCP (pKa = 4.74), in solid argon probably leads to the formation of two types of hydrogen bonded complexes: an ionic complex with the proton transferred to the amine molecule and a pseudosymmetric one with the proton more or less equally shared between the phenol and amine molecules. In this case the protonic absorption consists of two broad features situated in the 3000–1600 cm?1 and 950–400 cm?1 regions due to the ν(NH+ O?) and ν(O H N) modes, respectively. |