Substitution, Addition, and Recombination Reactions of Precursor Complexes with Ferrocenyl Carboxylate Units
Substitution, Addition, and Recombination Reactions of Precursor Complexes with Ferrocenyl Carboxylate Units
复制标题
DOI：
10.1002/ejic.200700542
复制
发表时间：
2007-11
影响因子：
2.3
通讯作者：
Xia Wang;Linke Li;H. Hou;Jie Wu;Yaoting Fan
中科院分区：
文献类型：
--
作者：
Xia Wang;Linke Li;H. Hou;Jie Wu;Yaoting Fan
以β-二茂铁基丙烯酸钠和对二茂铁基苯甲酸钠为功能配体，合成了含易离基团或配位不饱和金属离子的单核前体配合物：[Cd(η2-OOCCH=CHFC)2(C2 H5OH)2](1)，[Cd(η2-OOCC 6 H4 FC)2-(η)2(H2O)]}(2)，{[Cd(OOCC 6 H4 FC)2(Phen)(H2O)]-(CH3 OH)}(3)，和([Zn(OOCC6H4Fc)2(Phen)](H2O)}(4)(phen=1，10-邻菲咯啉))。对四种前驱体二茂铁羧酸盐配合物进行了研究，得到了十个配合物。配合物{[Cd(η2-OOCCH=CHFC)2(Bbbm)](H2O))n(1a)，{[Cd(η2-OOCCH=CHFC)4(Pbbm)2](CH30H)6(H20)4)(1b)，{[Cd(η2-OOCC6 H4FC)2(Py)3](CH3ΟH)4)(2a)，([Cd(η2-OOCC6H4Fc)4-(BTX)2](THf)3(CH30H)2}(2b)，在温和条件下，通过取代或加成反应合成了[Cd_2(η_2-OOCC6H_4Fc)_2(OOCC6H_4Fc)_2(Phen)_2(Phen)_2(Bbbm)](CH3_Ο_H)_4(Thf)_2)(3a)和[Zn(OOCC_6H_4fc)_2(Phen)(H20)](4a)。正如预期的那样，从前体到这些络合物都可以保持前体络合物的结构完整性。我们通过控制前驱体络合物中离开基团的数量来设计络合物的结构。此外，在苛刻的条件下，前体化合物与有机配体的反应可能发生了复合。“重组”配合物([CD2(η2-OOCCH=CHFC)2(μ2-η2-OOCCH=CHFC)2(L)2](CH30H)4)n[L=1，4-二(咪唑-1-甲基)苯(Bix)，1c；在回流条件下，L=btx，1d，([Cd(η2-OOCC 6 H4 FC)2-(Pbbm)(H2Ο)](H2Ο))n(3b)和([Zn(OOCC 6 H4 FC)2-(Bbbm)](CH3 OH)3)n(4b)。
With the use of sodium β-ferrocenylacrylate and sodium p-ferrocenylbenzoate as functional ligands, we synthesized mononuclear precursor complexes containing facile leaving groups or coordinatively unsaturated metal ions: [Cd(η 2 -OOCCH=CHFc)2(C 2 H 5 OH)2] (1), ([Cd(η 2 -OOCC 6 H 4 FC) 2 -(dmf) 2 (H 2 O)]} (2), {[(Cd(η 2 -OOCC 6 H 4 FC) 2 (Phen)(H 2 O)]-(CH 3 OH)} (3), and ([Zn(OOCC6H4Fc)2(phen)](H 2 O)} (4) (phen = 1,10-phenanthroline). Investigation of the four precursor ferrocenyl carboxylate complexes as building blocks resulted in ten complexes. The complexes {[Cd(η 2 -OOCCH=CHFC)2(bbbm)](H 2 O))n (1a), {[Cd 2 (η 2 -OOCCH=CHFc) 4 (pbbm)2](CH30H)6(H20)4) (1b), {[Cd(η 2 -OOCC 6 H 4 Fc) 2 (py) 3 ] (CH 3 ΟH) 4 ) (2a), ([Cd2(η 2 -OOCC6H4Fc)4-(btx)2](thf)3(CH30H) 2 } (2b), ([Cd2(η 2 -OOCC6H4Fc)2-(OOCC6H4Fc)2(phen)2(bbbm)] (CH 3 ΟH) 4 (thf) 2 ) (3a), and [Zn(OOCC 6 H 4 Fc)2(phen)(H20)] (4a) were obtained by the substitution or addition reactions of the precursor complexes under moderate conditions. As anticipated, the structural integrity of the precursor complexes can be maintained from the precursors to these complexes. We designed the structures of the complexes by controlling the number of leaving groups in the precursor complexes. In addition, a recombination may have taken place in the reactions of the precursor complexes with organic ligands under severe conditions. The "recombinant" complexes ([Cd 2 (η 2 -OOCCH=CHFc} 2 (μ 2 -η 2 -OOCCH=CHFc)2(L) 2 ](CH30H)4)n [L = 1,4-bis(imidazol-1-yl-methyl)benzene (bix), 1c; L = btx, 1d], ([Cd(η 2 -OOCC 6 H 4 FC) 2 -(pbbm)(H 2 Ο)](H 2 Ο)) n (3b) and ([Zn(OOCC 6 H 4 Fc) 2 -(bbbm)](CH 3 OH) 3 ) n (4b) were also obtained under reflux conditions.