Investigating the exceptional adducts of alkoxides with Ru(II)-arene cations in alkyl alcohol solution using electrospray ionization mass spectrometry.

Abstract

Exploring the formation mechanism of the exceptional adducts of alkoxides with Ru(II)-arene cations in alkyl alcohol solution using electrospray ionization mass spectrometry (ESI-MS) is crucial for further understanding the physicochemical properties of Ru(II)-arene complexes in solution. All mass spectra were collected with an AB SCIEX TripleTOF 5600+ mass spectrometer in positive mode. Theoretical calculations were carried out using the density functional theory method at the B3LYP level with a hybrid basis set consisting of 6-31G(d,p) and LanL2DZ in the Gaussian 03 program. When ruthenated [15 ]paracyclophanes (Ru-[15 ]PCPs) and Ru(II)-arene dimers were dissolved in alkyl alcohol solvents, the adducts of alkoxides with Ru(II)-arene cations were observed under positive ion mode ESI-MS, which resulted from the coordination of alkyl alcohol molecules with the Ru(II)-arene cations followed by the deprotonation of O-H bonds of the coordinated alcohols. Furthermore, the number of alkoxides binding to Ru-[15 ]PCPs was regulated by the number of ruthenium atoms. Attributed to good solubility and small steric hindrance, the signal intensity of the adducts of methoxides with Ru(II)-arene cations was the strongest among the three alkyl alcohols used in this study. The characteristic adducts of alkoxides with Ru(II)-arene cations were pervasively present in positive ion mode ESI-MS of nine Ru(II)-arene complexes dissolved in alkyl alcohol solvents. Taking into consideration the solubility and signal response, methanol is the most suitable solvent for the ESI-MS experiments with Ru(II)-arene complexes among the solvents studied, where almost only the diagnostic adducts of methoxides with Ru(II)-arene cations are present.