Department of Organic Chemistry, Charles University in Prague, Prague, Czech Republic.
Inorg Chem. 2011 Apr 4;50(7):3153-8. doi: 10.1021/ic2002767. Epub 2011 Mar 7.
The effect of different modes of the carboxylato ligands on the reactivity of gaseous zinc-acetate complexes is reported. Using infrared multiphoton dissociation spectroscopy, it is demonstrated that the coordination of acetate in (Imi)(n)Zn(CH(3)COO) complexes (Imi = imidazole, n = 1-3) changes from bi- to monodentate upon coordination of the third imidazole ligand. This so-called carboxylate shift substantially influences the reactivity of the zinc-acetate complexes in comparison to complexes with monodentate counterions. The differences in reactivities are demonstrated on the ligand exchange reactions of L(n)ZnX (n = 2 or 3,; L = imidazole or pyridine; X = OH, Cl, CH(3)COO, and CH(3)CONHO).
报道了羧基配体的不同模式对气态乙酸锌配合物反应性的影响。利用红外多光子解离光谱，证明了在(Imi)(n)Zn(CH(3)COO)配合物（Imi = 咪唑，n = 1-3）中，当第三个咪唑配体配位时，乙酸根的配位从双齿变为单齿。与具有单齿抗衡离子的配合物相比，这种所谓的羧酸盐转移极大地影响了乙酸锌配合物的反应性。通过L(n)ZnX（n = 2 或 3；L = 咪唑或吡啶；X = OH、Cl、CH(3)COO 和 CH(3)CONHO）的配体交换反应证明了这些差异。
