The hydrolysis of cyanophenols at a bimetallic Re 2(III, III) core

Abstract

Studies of nitrile hydrolysis at the dirhenium core of [N(C 4H 9) 4] 2[Re 2Cl 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(C 4H 9) 4] 2[Re 2Cl 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(C 4H 9) 4][Re 2Cl 6(2-HOC 6H 4NHC(O))] ( 1), [N(C 4H 9) 4][Re 2Cl 6(3-HOC 6H 4NHC(O))] ( 2), and [N(C 4H 9) 4][Re 2Cl 6(4-HOC 6H 4NHC(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(C 4H 9) 4] 2[Re 2Cl 8] in methylene chloride:alcohol solvent mixtures, and using AgBF 4 and thallium(I) triflate (TlO 3SCF 3) to promote chloride removal in order to compare the general reaction times and yields.