Synthesis and Coordination Properties of Chelating Dithiophenolate Ligands
Synthesis and Coordination Properties of Chelating Dithiophenolate Ligands
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DOI：
10.1021/ic801285u
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发表时间：
2009-01-05
影响因子：
4.6
通讯作者：
Meyer, Franc
中科院分区：
文献类型：
--
作者：
Ballmann, Joachim;Fuchs, Michael G. G.;Meyer, Franc
3，3‘-R-1-5，5’-R-2-2，2‘-二硫联苯配体(R-1=R-2=Cl，4a；R-1=R-2=Bu-t，4b；R-1=烯丙基，R-2=H，4c)和2，2’-亚甲基二苯硫醇配体(4d)由相应的二醇(1a-1d)通过宫崎-纽曼-库尔特重排三步反应合成。为了探索它们的配位潜力，合成了锌配合物和锡配合物(4C)，取代方式和螯合环的大小严重影响了它们的配位性能。对其中四个配合物进行了固态结晶学表征，并用扩散有序核磁共振法研究了锌配合物在溶液中的成核性。根据配体的不同，锌配合物[(4)锌(4，4‘-丁基-t-联吡啶)](N)(5a-d)可以是单体(n=1；4b，4c)、溶液中的单体和固体中的二聚体(n=1，2；4a)，或者是整体的二聚体(n=2；4d)。另外还合成了锡络合物(4c)SnPh2(6c)，证明了烯丙基取代配体4c的配位能力。
Chelating 3,3'-R-1-5,5'-R-2 -2,2'-dithiobiphenyl ligands (R-1 = R-2 = Cl, 4a; R-1 = R-2 = Bu-t, 4b; R-1 = allyl, R-2 = H, 4c) and the 2,2'-methylenedibenzenethiol ligand (4d) were synthesized from the corresponding diols (1a-1d) via a three-step procedure involving a Miyazaki-Newman-Kwart rearrangement. Zinc complexes and a tin complex (for 4c) have been prepared to explore their coordination potential, and the substitution pattern, as well as the chelate ring size, is shown to severely effect their ligating properties. Four of the complexes have been characterized crystallographically in the solid state, and the nuclearity of the zinc complexes in solution has been studied by diffusion-ordered NMR spectroscopy. Depending on the ligand, zinc complexes [(4)Zn(4,4'-Bu-t-bipyridine)](n) (5a-d) are monomeric (n = 1; 4b, 4c), monomeric in solution and dimeric in the solid state (n = 1, 2; 4a), or dimeric overall (n = 2; 4d). The tin complex (4c)SnPh2 (6c) was additionally synthesized to prove the coordinating abilities of the allyl substituted ligand 4c.