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Stable “Inverse” Sandwich Complex with Unprecedented Organocalcium(I): Crystal Structures of [(thf)2Mg(Br)-C6H2-2,4,6-Ph3] and [(thf)3Ca{μ-C6H3-1,3,5-Ph3}Ca(thf)3]
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-03-04 , DOI: 10.1021/ja808524y Sven Krieck 1 , Helmar Görls 1 , Lian Yu 1 , Markus Reiher 1 , Matthias Westerhausen 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-03-04 , DOI: 10.1021/ja808524y Sven Krieck 1 , Helmar Görls 1 , Lian Yu 1 , Markus Reiher 1 , Matthias Westerhausen 1
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The reaction of bromo-2,4,6-triphenylbenzene with activated magnesium in THF yielded the Grignard reagent [(thf)(2)Mg(Br)-C(6)H(2)-2,4,6-Ph(3)] (1) with a Mg-C bond length of 214.8(3) pm. A similar reaction of bromo-2,4,6-triphenylbenzene with activated calcium led to an "inverse" sandwich complex [(thf)(3)Ca{mu-C(6)H(3)-1,3,5-Ph(3)}Ca(thf)(3)] (2) with the calcium atoms on opposite sides of the central arene ring showing small Ca-Ca' and Ca-C distances of 427.9(3) and 259.2(3) pm. This extremely air- and moisture-sensitive complex exhibits thermochomic and solvatochromic behavior. It is paramagnetic with spin of S = 1 (triplet) with an ESR resonance at g = 2.0023. Quantum chemical calculations shed light on the bonding situation in this very unusual dinuclear Ca(I) compound.
中文翻译：
具有前所未有的有机钙 (I) 的稳定“反向”三明治复合物：[(thf)2Mg(Br)-C6H2-2,4,6-Ph3] 和 [(thf)3Ca{μ-C6H3-1,3, 5-Ph3}Ca(thf)3]
溴-2,4,6-三苯苯与活化镁在 THF 中反应生成格氏试剂 [(thf)(2)Mg(Br)-C(6)H(2)-2,4,6-Ph( 3)] (1) Mg-C 键长为 214.8(3) pm。溴-2,4,6-三苯苯与活化钙的类似反应导致“反向”夹心复合物 [(thf)(3)Ca{mu-C(6)H(3)-1,3,5- Ph(3)}Ca(thf)(3)] (2) 中心芳烃环两侧的钙原子显示出较小的 Ca-Ca' 和 Ca-C 距离，分别为 427.9(3) 和 259.2(3) pm . 这种对空气和水分极为敏感的复合物表现出热致变色和溶剂致变色行为。它是顺磁性的，自旋 S = 1（三重态），在 g = 2.0023 处有 ESR 共振。量子化学计算揭示了这种非常不寻常的双核 Ca(I) 化合物中的键合情况。
更新日期：2009-03-04
中文翻译：
具有前所未有的有机钙 (I) 的稳定“反向”三明治复合物：[(thf)2Mg(Br)-C6H2-2,4,6-Ph3] 和 [(thf)3Ca{μ-C6H3-1,3, 5-Ph3}Ca(thf)3]
溴-2,4,6-三苯苯与活化镁在 THF 中反应生成格氏试剂 [(thf)(2)Mg(Br)-C(6)H(2)-2,4,6-Ph( 3)] (1) Mg-C 键长为 214.8(3) pm。溴-2,4,6-三苯苯与活化钙的类似反应导致“反向”夹心复合物 [(thf)(3)Ca{mu-C(6)H(3)-1,3,5- Ph(3)}Ca(thf)(3)] (2) 中心芳烃环两侧的钙原子显示出较小的 Ca-Ca' 和 Ca-C 距离，分别为 427.9(3) 和 259.2(3) pm . 这种对空气和水分极为敏感的复合物表现出热致变色和溶剂致变色行为。它是顺磁性的，自旋 S = 1（三重态），在 g = 2.0023 处有 ESR 共振。量子化学计算揭示了这种非常不寻常的双核 Ca(I) 化合物中的键合情况。
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