Strohmann Carsten, Strohfeldt Katja, Schildbach Daniel
Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
J Am Chem Soc. 2003 Nov 12;125(45):13672-3. doi: 10.1021/ja0374372.
The crystal structures of the two chiral alkyllithium bases [n-BuLi.(-)-sparteine]2 (1) and [Et2O.(i-PrLi)2.(-)-sparteine] (2) have been determined. For compound 1, a symmetric dimer is observed in the solid state, with two (-)-sparteine ligands coordinating to the lithium centers. Because of steric reasons, compound 2 crystallizes as an unsymmetric dimer with the four methyl groups pointing away from the sterically demanding (-)-sparteine ligand. Compound 2 contains one four-coordinate lithium center [coordinated to (-)-sparteine] and one three-coordinate lithium center (coordinated to Et2O). As a result of this arrangement, significantly different Li-C distances are found in the central four-membered ring of compound 2.
已确定两种手性烷基锂碱[n-BuLi·(-)-鹰爪豆碱]₂ (1) 和 [Et₂O·(i-PrLi)₂·(-)-鹰爪豆碱] (2) 的晶体结构。对于化合物1,在固态中观察到一个对称二聚体,有两个(-)-鹰爪豆碱配体与锂中心配位。由于空间位阻原因,化合物2结晶为不对称二聚体,四个甲基远离空间位阻较大的(-)-鹰爪豆碱配体。化合物2包含一个四配位锂中心[与(-)-鹰爪豆碱配位]和一个三配位锂中心(与Et₂O配位)。由于这种排列,在化合物2的中心四元环中发现了明显不同的Li-C距离。