Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
Dalton Trans. 2012 Aug 7;41(29):8941-50. doi: 10.1039/c2dt30609c. Epub 2012 Jun 20.
The [N(2)S(2)]-type ligand 1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4) (L) is prepared in 84% yield by a new method and its structure has been confirmed by X-ray crystallography. The new synthetic method involves sequential reaction of 1,2-phenylenedithiol with EtONa followed by treatment of the resulting disodium salt of 1,2-phenylenedithiol with in situ generated 2-(chloromethyl)pyridine from its HCl salt. Further treatment of ligand L with NiCl(2)·6H(2)O or NiI(2) affords the expected new mononuclear Ni complexes Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Cl(2) (1) and Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]I(2) (3) in 87-88% yields, whereas reaction of L with NiBr(2) under similar conditions results in formation of the expected new mononuclear complex Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Br(2) (2) and one unexpected new mononuclear complex Ni[1-(2-C(5)H(4)NCH(2)S)-2-(2-C(5)H(4)NCH(2)SC(6)H(4)S)C(6)H(4)]Br(2) (2*) in 82% and 5% yields, respectively. More interestingly, the ligand L-containing novel trinuclear NiFe(2) complex Ni{[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)}Fe(2)(CO)(6)(μ(3)-S)(2) (4) is found to be prepared by sequential reaction of (μ-S(2))Fe(2)(CO)(6) with Et(3)BHLi, followed by treatment of the resulting (μ-LiS)(2)Fe(2)(CO)(6) with mononuclear complex 1, 2, or 3 in 12-20% yields. The new complexes 1-4 and 2* are fully characterized by elemental analysis and various spectroscopies, and the crystal structures of 1, 2* and 3 as well as some electrochemical properties of 1-4 are also reported.
[N(2)S(2)]-型配体 1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4) (L) 通过一种新方法以 84%的产率制备，并通过 X 射线晶体学确证其结构。新的合成方法涉及 1,2-苯二硫醇与 EtONa 的连续反应，然后用原位生成的 2-(氯甲基)吡啶处理由此 HCl 盐生成的 1,2-苯二硫醇的二钠盐。配体 L 与 NiCl(2)·6H(2)O 或 NiI(2)进一步反应以 87-88%的产率得到预期的新型单核 Ni 配合物 Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Cl(2) (1) 和 Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]I(2) (3)，而在类似条件下 L 与 NiBr(2)的反应则生成预期的新型单核配合物 Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Br(2) (2) 和一个意外的新型单核配合物 Ni[1-(2-C(5)H(4)NCH(2)S)-2-(2-C(5)H(4)NCH(2)SC(6)H(4)S)C(6)H(4)]Br(2) (2*)，分别以 82%和 5%的产率得到。更有趣的是，发现含有配体 L 的新型三核 NiFe(2)配合物 Ni{[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)}Fe(2)(CO)(6)(μ(3)-S)(2) (4) 是通过(μ-S(2))Fe(2)(CO)(6)与 Et(3)BHLi 的连续反应制备的，然后用单核配合物 1、2 或 3处理所得(μ-LiS)(2)Fe(2)(CO)(6)，以 12-20%的产率得到。新的配合物 1-4 和 2* 通过元素分析和各种光谱学方法进行了充分的表征，并报道了 1、2*和 3 的晶体结构以及 1-4 的一些电化学性质。
