Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Canada.
Dalton Trans. 2011 May 14;40(18):5009-17. doi: 10.1039/c1dt00018g. Epub 2011 Mar 30.
Btzn (1), an amine-functionalized bi(1,3,5-triazine) 4,4'-(NH(2))(2)-6,6'-(NHC(6)H(5))(2)-2,2'-(1,3,5-C(3)N(3))(2), is reported, and its coordination with Co, Ni and Cu is explored. Reactions of metal salts (2 equiv) with Btzn (1 equiv) result in dimeric species [(Btzn)Co(2)(NCS)(4)(EtOH)(2)(DMF)(2)], (2), [(Btzn)Ni(2)(η(1)-ONO(2))(2)(MeOH)(4)(DMF)(2)]·2[NO(3)], (3), [(Btzn)Cu(2)Cl(4)(DMF)(2)], (4), and [(Btzn)Cu(2)(η(2)-O(2)NO)(2)(OH(2))(2)(DMF)(2)]·2[NO(3)], (5). These complexes are the first examples of the coordination of transition metals with bi(1,3,5-triazine) ligands. Their structures display a bridging bis-bidentate coordination mode for Btzn. Variable-temperature magnetic susceptibility of the complexes reveals antiferromagnetic exchange between the spin carriers, with calculated exchange coupling values (J) of -4.7 cm(-1) for 3, -18.2 cm(-1) for 4, and -5.5 cm(-1) for 5. An in-depth evaluation of the metal geometry highlights the inefficient overlap of the magnetic d-orbitals through the bridging ligand, most likely leading to reduced delocalization and coupling.
报道了一种胺功能化的双（1,3,5-三嗪）4,4'-(NH(2))(2)-6,6'-(NHC(6)H(5))(2)-2,2'-(1,3,5-C(3)N(3))(2), 并探索了其与 Co、Ni 和 Cu 的配位。金属盐（2 当量）与 Btzn（1 当量）反应生成二聚体 [(Btzn)Co(2)(NCS)(4)(EtOH)(2)(DMF)(2)], (2), [(Btzn)Ni(2)(η(1)-ONO(2))(2)(MeOH)(4)(DMF)(2)]·2[NO(3)], (3), [(Btzn)Cu(2)Cl(4)(DMF)(2)], (4), 和 [(Btzn)Cu(2)(η(2)-O(2)NO)(2)(OH(2))(2)(DMF)(2)]·2[NO(3)], (5)。这些配合物是首例过渡金属与双（1,3,5-三嗪）配体配位的例子。它们的结构显示 Btzn 采用桥联双齿配位模式。配合物的变温磁化率表明自旋载体之间存在反铁磁交换，计算得到的交换耦合值 (J) 为-4.7 cm(-1)（3）、-18.2 cm(-1)（4）和-5.5 cm(-1)（5）。对金属几何形状的深入评估表明，通过桥联配体，磁 d 轨道的重叠效率不高，这很可能导致离域和耦合减少。
