The hydrolysis of cyanophenols at a bimetallic Re₂(III, III) core

Studies of nitrile hydrolysis at the dirhenium core of [N(C₄H₉)₄]₂[Re₂Cl ₈] were extended through both the inclusion of a series of substituted nitriles, 2-, 3-, and 4-cyanophenol and either silver or thallium salts to promote the removal of chloride from [N(C₄H₉)₄]₂[Re₂Cl ₈]. Based on the expanded studies, steric limitations resulting from the -OH group are not evident in the hydrolysis reaction for this series of benzonitriles, and the reaction resulted in the synthesis of bridging amidate ligands coordinated to the dirhenium core in [N(C₄H₉)₄][Re₂Cl₆ (2-HOC₆H₄NHC(O))] (1), [N(C₄H₉)₄][Re₂Cl₆ (3-HOC₆H₄NHC(O))] (2), and [N(C₄H₉)₄][Re₂Cl₆ (4-HOC₆H₄NHC(O))] (3), respectively. In addition to the structural and spectroscopic characterization of the series of compounds, the reactions were performed by simply heating the nitrile and [N(C₄H₉)₄]₂[Re₂Cl ₈] in methylene chloride:alcohol solvent mixtures, and using AgBF₄ and thallium(I) triflate (TlO₃SCF₃) to promote chloride removal in order to compare the general reaction times and yields.