Boyle Timothy J, Andrews Nicholas L, Rodriguez Mark A, Campana Charles, Yiu Timothy
Advanced Materials Laboratory, Sandia National Laboratories, 1001 University Boulevard SE, Albuquerque, New Mexico 87106, USA.
Inorg Chem. 2003 Aug 25;42(17):5357-66. doi: 10.1021/ic034222k.
A series of potassium aryloxides (KOAr) were isolated from the reaction of a potassium amide (KN(SiMe(3))(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: ([K(mu(4)-oMP)(THF)][K(mu(3)-oMP)])(5) (1), [K(6)(eta(6),mu(3)-oMP)(4)(eta(6),mu(4)-oMP)(2)(py)(4)].[K(6)(eta(6),mu(3)-oMP)(6)(eta(6)-py)(4)] (2), K(mu(3)-oPP)(THF)(3) (3), K(4)(eta(6),mu(3)-oPP)(2)(mu(3)-oPP)(2)(py)(3) (4), K(mu(3)-oBP)(THF) (5), K(6)(eta(6),mu(3)-oBP)(2)(mu(3)-oBP)(4)(py)(4) (6), K(3)(eta(6),mu(3)-DMP)(2)(mu-DMP)(THF) (7), K(eta(6),mu-DMP)(py) (8), K(eta(6),mu-DIP) (9), K(eta(6),mu-DBP) (10). Further exploration of the aryl interactions led to the investigation of the diphenylethoxide (DPE) derivative which was isolated as K(mu(3)-DPE)(THF) (11) or K(mu(3)-DPE)(py).py(2) (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 pi-bound to the aryl rings of the neighboring phenoxide derivatives to fill their coordination sites. The synthesss and characterization of these compounds are described in detail.
通过在四氢呋喃（THF）或吡啶（py）中，使氨基钾（KN(SiMe(3))(2)）与所需的取代酚盐（邻甲基酚盐，oMP，2 - 甲基；邻异丙基酚盐，oPP，2 - 异丙基；邻叔丁基酚盐，oBP，2 - 叔丁基；2,6 - 二甲基酚盐，DMP；2,6 - 二异丙基酚盐，DIP；2,6 - 二叔丁基酚盐，DBP）反应，分离得到了一系列芳氧基钾（KOAr），如下所示：([K(μ(4)-oMP)(THF)][K(μ(3)-oMP)])(5) (1)，[K(6)(η(6),μ(3)-oMP)(4)(η(6),μ(4)-oMP)(2)(py)(4)].[K(6)(η(6),μ(3)-oMP)(6)(η(6)-py)(4)] (2)，K(μ(3)-oPP)(THF)(3) (3)，K(4)(η(6),μ(3)-oPP)(2)(μ(3)-oPP)(2)(py)(3) (4)，K(μ(3)-oBP)(THF) (5)，K(6)(η(6),μ(3)-oBP)(2)(μ(3)-oBP)(4)(py)(4) (6)，K(3)(η(6),μ(3)-DMP)(2)(μ-DMP)(THF) (7)，K(η(6),μ-DMP)(py) (8)，K(η(6),μ-DIP) (9)，K(η(6),μ-DBP) (10)。对芳基相互作用的进一步探索导致了对二苯乙醇盐（DPE）衍生物的研究，根据所使用的溶剂不同，其分离形式为K(μ(3)-DPE)(THF) (11) 或 K(μ(3)-DPE)(py).py(2) (12)。一般来说，空间位阻较小的配体（oMP、oPP、oBP和DMP）形成溶剂化聚合物物种；然而，空间位阻增大（DIP和DBP）则导致非溶剂化聚合物而非离散分子。对于这个新型化合物家族中的大多数，K原子与相邻酚盐衍生物的芳环形成π键以填充其配位位点。详细描述了这些化合物的合成与表征。
