A straightforward catalytic approach to obtain deuterated chloroform at room temperature.

We report the catalytic activity for the complexes - cis-[RuCl2 (dppb)(bipy)] (A), and [η6 -(p-cymene)Ru (dppb)Cl]PF6 (B), wherein dppb = 1,4-bis (diphenylphosphine)butane, and bipy = 2,2'-bipyridine - for the synthesis of CDCl3 from CHCl3 using D2 O as deuterium source. H/D exchange reactions were performed using a chloroform/D2 O, 1:2 molar ratio, vigorously stirred, at room temperature. 1 mol of KOH was dissolved in D2 O fraction and catalytic complexes from 0.002 to 0.05 mmol were dissolved in chloroform. The H/D exchange reactions were monitored using 13 C NMR sequences without proton decoupling. The reaction using 0.01 mmol of compound A reached approximately 55% of H/D conversion in one hour. In the same time, the reactions with 0.002 mmol of compound A and without catalyst, show approximately 28% and 3% H/D exchange, respectively. Without the catalysts, the H/D exchange was only 12.0% in 5 hours. For compound B, 55% H/D conversion was observed in 1 hour, only when 0.05 mmol was used, which is much higher catalyst concentration. After the isolation of the chloroform fraction and two more addition of D2 O it was possible to obtain 95.0% H/D exchange in approximately 3 hours, using 0.01 mmol of the compound A. Therefore, compound A is an efficient catalyst for a rapid and straightforward synthesis of CDCl3 from CHCl3 at room temperature and using D2 O as deuterium source.