Publications

Structural variations of potassium aryloxides

Boyle, Timothy J.; Boyle, Timothy J.; Andrews, Nicholas L.; Rodriguez, Marko A.

A series of potassium aryloxides (KOAr) were isolated from the reaction of a potassium amide (KN(SiMe3)2) and the desired substituted phenoxide (oMP, 2-methyl; oPP, 2-iso-propyl; oBP, 2-tert-butyl; DMP, 2,6-di-methyl; DIP, 2,6-di-iso-propyl; DBP, 2,6-di-tert-butyl) in tetrahydrofuran (THF) or pyridine (py) as the following: {l_brace}([K(4-oMP)(THF)][K(3-oMP)])5{r_brace} (1), {l_brace}[K6(6,3-oMP)4(6,4-oMP)2(py)4] {center_dot} [K6(6,3-oMP)6(6-py)4]{r_brace} (2), [K(3-oPP)]4(THF)3 (3), {l_brace}K4(6,3-oPP)2(3-oPP)2(py)3{r_brace} (4), [K(3-oBP)(THF)]6 (5), {l_brace}K6(6,3-oBP)2(3-oBP)4(py)4{r_brace} (6), {l_brace}K3(6,3-DMP)2(-DMP)(THF){r_brace} (7), {l_brace}[K(6,-DMP)(py)]2{r_brace} (8), {l_brace}K(6,-DIP){r_brace} (9), {l_brace}K(6,-DBP){r_brace} (10). Further exploration of the aryl interactions led to the investigation of the diphenylethoxide (DPE) derivative which was isolated as [K(3-DPE)(THF)]4 (11) or [K(3-DPE)(py)]4 {center_dot} py2 (12) depending on the solvent used. In general, the less sterically demanding ligands (oMP, oPP, oBP, and DMP) were solvated polymeric species; however, increasing the steric bulk (DIP and DBP) led to unsolvated polymers and not discrete molecules. For most of this novel family of compounds, the K atoms were -bound to the aryl rings of the neighboring phenoxide derivatives to fill their coordination sites. The synthesis and characterization of these compounds are described in detail.