Structural Diversity in a Series of Alkyl-Substituted Cesium Aryloxides

• Published in: Inorganic chemistry Vol. 50; no. 20; pp. 10363 - 10370
• Main Authors: Boyle, Timothy J, Steele, Leigh Anna M, Saad, Alia M, Rodriguez, Mark A, Alam, Todd M, McIntyre, Sarah K
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17.10.2011
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic201438s

A family of cesium aryloxides [Cs(OAr)] n were synthesized and structurally characterized from the reaction of 1:1 or 1:excess stoichiometry of Cs0 and the appropriate alkyl-substituted phenol: 2-alkylphenol [alkyl = methyl (H-oMP), isopropyl (H-oPP), and tert-butyl (H-oBP)] and 2,6-dialkylphenol [alkyl = methyl (H-DMP), isopropyl (H-DIP), tert-butyl (H-DBP), and phenyl (H-DPhP)]. The products were structurally identified as [Cs(oMP)(H-oMP)2] n (1), [Cs5(oPP)5] n (2), [Cs4(oBP)4(H-oBP)6] n (3x, shown), [Cs3(DMP)3] n (4), [Cs2(DIP)2] n (5), [Cs(DIP)(H-DIP)] n (5x), and [Cs(DPhP)] n (7). Compounds 1–7 were found to adopt complex polymeric structures employing π interactions from the neighboring pendant phenoxide ligands. The solution behavior of these compounds was studied using solution 133Cs NMR spectroscopy, and for each compound, a single 133Cs NMR resonance was observed, with chemical shift values found to be strongly solvent-dependent. This implies that monomeric cesium salt species involving solvent interactions exist in solution.