Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, August-Bebel-Strasse 2, D-07743 Jena, Germany.
Chem Asian J. 2010 Feb 1;5(2):272-7. doi: 10.1002/asia.200900552.
The addition of [(L)(4)Ca(I)Mes] (Lewis base L=thf, Et(2)O) to mesityl copper(I) and the transmetalation reaction of mesityl copper(I) with activated calcium are suitable pathways for the synthesis of dimesityl cuprates(I) of calcium. However, the structures of the calcium cuprates(I) depend on the preparative procedure. The transmetalation reaction leads to the formation of Mes-Cu-Mes anions whereas the addition yields dinuclear (Mes-Cu)(2)(mu-Mes) anions. The solvent-separated counterions are Ca(thf)(6) and (thf)(5)CaI, respectively. In contrast to these findings, the addition of [(L)(4)Ca(I)Mes] to mesityl copper(I) in an Et(2)O/toluene mixture led to formation of tetrameric solvent-free iodocalcium dimesityl cuprate(I) ICa(mu-eta(1),eta(6)-Mes(2)Cu), representing a rare example of a heavy Normant-type organocuprate.
将 [(L)(4)Ca(I)Mes]（路易斯碱 L=thf、Et(2)O）添加到均三甲基金属铜 (I) 中，以及均三甲基金属铜 (I) 与活性钙的转金属反应，是合成钙二甲基铜 (I) 的合适途径。然而，钙铜酸盐 (I) 的结构取决于制备程序。转金属反应导致 Mes-Cu-Mes阴离子的形成，而添加则生成双核 (Mes-Cu)(2)(mu-Mes)阴离子。溶剂分离的抗衡离子分别为 Ca(thf)(6)和 (thf)(5)CaI。与这些发现相反，将 [(L)(4)Ca(I)Mes] 添加到均三甲基金属铜 (I) 在 Et(2)O/甲苯混合物中导致形成无溶剂四聚体碘化钙二甲基铜 (I) ICa(mu-eta(1),eta(6)-Mes(2)Cu)，这代表了重Normant 型有机铜的罕见例子。
