Graziano Brendan J, Wile Bradley M, Zeller Matthias
Donald J. Bettinger Department of Chemistry and Biochemistry, Ohio Northern University, 525 S. Main Street, Ada, Ohio 45810, USA.
Department of Chemistry, Purdue University, 560 Oval Dr., West Lafayette, Indiana 47907, USA.
Acta Crystallogr E Crystallogr Commun. 2019 Jul 26;75(Pt 8):1265-1269. doi: 10.1107/S2056989019010454. eCollection 2019 Aug 1.
Bidentate and tridentate coordination of a 2,4-di--butyl-substituted bridging amine bis-(phenolate) ligand to a palladium(II) center are observed within the same crystal structure, namely di-chlorido-({6,6'-[(ethane-1,2-diylbis(methyl-aza-nedi-yl)]bis-(methyl-ene)}bis-(2,4-di--butyl-phenol))palladium(II) chlorido-(2,4-di--butyl-6-{[(2-{(3,5-di--butyl-2-hy-droxy-phen-yl)meth-ylamino}-eth-yl)(meth-yl)amino]-meth-yl}phenolato)palladium(II) methanol 1.685-solvate 0.315-hydrate, [PdCl(CHNO)][PdCl(CHNO)]·1.685CHOH·0.315HO. Both complexes exhibit a square-planar geometry, with unbound phenol moieties participating in inter-molecular hydrogen bonding with co-crystallized water and methanol. The presence of both κ and κ coordination modes arising from the same solution suggest a dynamic process in which phenol donors may coordinate or dissociate from the metal center, and offers insight into catalyst speciation throughout Pd-mediated processes. The unit cell contains di-chlorido-({6,6'-[(ethane-1,2-diylbis(methyl-aza-nedi-yl)]bis-(methyl-ene)}bis-(2,4-di--butyl-phenol))palladium(II), {( )PdCl}, and chlorido-(2,4-di--butyl-6-{[(2-{(3,5-di--butyl-2-hy-droxy-phen-yl)meth-ylamino}eth-yl)(meth-yl)amino]-meth-yl}phenolato)palladium(II), {( )PdCl}, mol-ecules as well as fractional water and methanol solvent mol-ecules.
在同一晶体结构中观察到2,4 - 二叔丁基取代的桥连胺双（酚盐）配体与钯（II）中心的双齿和三齿配位，即二氯 - （{6,6'-[（乙烷 - 1,2 - 二基双（甲基 - 氮杂二基）]双（亚甲基）}双（2,4 - 二叔丁基苯酚））钯（II）氯 - （2,4 - 二叔丁基 - 6 - {[（2 - {[（3,5 - 二叔丁基 - 2 - 羟基苯基）甲基]（甲基）氨基}乙基）（甲基）氨基]甲基}苯酚根）钯（II）甲醇1.685溶剂合物0.315水合物，[PdCl(CHNO)][PdCl(CHNO)]·1.685CHOH·0.315HO。两种配合物均呈现平面正方形几何构型，未配位的酚基部分与共结晶的水和甲醇参与分子间氢键作用。来自同一溶液中κ和κ配位模式的共存表明存在一种动态过程，其中酚供体可能与金属中心配位或解离，这为深入了解整个钯介导过程中的催化剂形态提供了线索。晶胞包含二氯 - （{6,6'-[（乙烷 - 1,2 - 二基双（甲基 - 氮杂二基）]双（亚甲基）}双（2,4 - 二叔丁基苯酚））钯（II），{( )PdCl}，以及氯 - （2,4 - 二叔丁基 - 6 - {[（2 - {[（3,5 - 二叔丁基 - 2 - 羟基苯基）甲基]（甲基）氨基}乙基）（甲基）氨基]甲基}苯酚根）钯（II），{( )PdCl}分子以及部分水和甲醇溶剂分子。
