Kinetics and mechanism of ligand substitution reactions of (2,6-diaminopyridine)[M(CO)5]2 (M = Cr, Mo, W)
作者:Khalil J. Asali、Mohammad El-khateeb、Laith Almazahreh
DOI:10.1007/s11243-015-9936-z
日期:2015.8
The bimetallic complexes (μ-2,6-dap)[M(CO)5]2 [2,6-dap = 2,6-diaminopyridine, M = Cr (1), Mo (2), W (3)] were synthesized from M(CO)6 and 2,6-diaminopyridine. The complexes were characterized on the basis of their carbonyl stretching frequencies and elemental analysis. A thermal kinetic study of the reactions of complexes 1–3 with P(OiPr)3 under pseudo-first-order reaction conditions in chlorobenzene
双金属配合物 (μ-2,6-dap)[M(CO)5]2 [2,6-dap = 2,6-二氨基吡啶, M = Cr (1), Mo (2), W (3)]由 M(CO)6 和 2,6-二氨基吡啶合成。根据它们的羰基伸缩频率和元素分析表征配合物。对配合物 1-3 与 P(OiPr)3 在拟一级反应条件下在氯苯中的反应进行了热动力学研究。这些反应通过两步机制进行,得到 M(CO)5 中间体,该中间体与 P(OiPr)3 迅速反应生成 M(CO)5(P(OiPr)3)。第一步,包括一个 M-N 键的初始解离以得到单金属 (2,6-dap)M(CO)5 和 M(CO)5,比第二个 M-N 键的解离慢得多因此是速率决定的。