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

Studies of nitrile hydrolysis at the dirhenium core of [N(C4H9)4]2[Re2Cl8] 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[Re2Cl8]. 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[Re2Cl8] 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.