Self-assembled chloro-bridged (arene)ruthenium metallo-prisms: Synthesis and molecular structure of cationic complexes of the type [Ru6(η6-arene)6(μ3-tpt-κN)2(μ-Cl)6]6+ (tpt=2,4,6-tris(pyridinyl)-1,3,5-triazine)
Self-assembled chloro-bridged (arene)ruthenium metallo-prisms: Synthesis and molecular structure of cationic complexes of the type [Ru6(η6-arene)6(μ3-tpt-κN)2(μ-Cl)6]6+ (tpt=2,4,6-tris(pyridinyl)-1,3,5-triazine)
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DOI：
10.1021/om060843k
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发表时间：
2007-02-12
期刊：
影响因子：
2.8
通讯作者：
Therrien, Bruno
中科院分区：
文献类型：
--
作者：
Govindaswamy, Padavattan;Suess-Fink, Georg;Therrien, Bruno
通过两个组分的自组装，以较高的产率合成了具有三棱柱结构的阳离子(芳烃)六核配合物[Ru(ETA(6)-芳烃)(Mu-Cl)Cl](2)(芳烃=p-(PrC6H4Me)-C-I，C6Me6)在水中与2，4，6-三(吡啶)-1，3，5-三嗪(TPT)衍生物在AgO3SCF3存在下形成通式[Ru-6(ETA(6)-芳烃)(6)(Mu(3)-TPT-kappa N)(2)(Mu-Cl)(6)](6+)的六核阳离子。在2，4，6-三(吡啶-4-基)-1，3，[Ru-6(eta(6)-p-(PrC6H4Me)-C-i)(6)(mu(3)-4-tpt-kappa N)(2)(Mu-Cl)(6)(6+)(3)和[Ru-6(Eta(6)-C6Me6)(6)(Mu(3)-4-Tpt-kappa N)(2)(Mu-Cl)(6)](6+)(4)作为三氟盐，6-三(吡啶-3-基)-1，3，5-三嗪(3-TPT)[Ru-6(eta(6)-p-(PrC6H4Me)-C-i)(6)(mu(3)-3-tpt-kappa N)(2)(Mu-Cl)(6)(6+)(7)和[Ru-6(EtA(6)-C6Me6)(6)(Mu(3)-3-TPT-kappa N)(2)(Mu-Cl)(6)](6+)(8)被分离为三氟盐。在所有情况下，最初在添加三氟化银之前形成的中性中间体也被分离和表征：[[Ru-3(eta(6)-p-(PrC6H4Me)-C-i)(3)(mu(3)-4-tpt-kappa N)Cl-6](1)，[Ru-3(Eta(6)-C6Me6)(3)(Mu(3)-4-TPT-kappa N)Cl-6](2)，[Ru-3(eta(6)-p-(PrC6H4Me)-C-i)(3)(mu(3)-3-tpt-kappa N)Cl-6](5)和[Ru-3(eta(6)-C6Me6)(3)(Mu(3)-3-TPT-kappa N)Cl-6](6)。在含有对伞花烃和3-TPT配体的三棱柱配位的情况下，核磁共振谱显示了两个异构体7a和7b的混合物，其形成可以通过分子模拟来合理地解释。[Ru-6(eta(6)-p-(PrC6H4Me)-C-i)(6)(mu(3)-4-tpt-kappa N)(2)(Mu-Cl)(6)][O3SCF3](6)([3][O3SCF3](6))的单晶结构分析，[RU-6(ETA(6)-C6Me6)(6)(Mu(3)-4-TPT-kappa N)(2)(Mu-Cl)(6)][O3SCF3](6)([4][O3SCF3](6))，和[Ru-6(ETA(6)-C6Me6)(6)(Mu(3)-3-TPT-kappa N)(2)(Mu-Cl)(6)][O3SCF3](6)([8][O3SCF3](6))显示了三棱柱的两个TPT亚基之间强烈的pi堆积作用。
Cationic (arene)ruthenium-based hexanuclear complexes with trigonal-prismatic structures have been synthesized in good yield by self-assembly of only two components: the dinuclear (arene)ruthenium complexes [Ru(eta(6)-arene)(mu-Cl)Cl](2) (arene = p-(PrC6H4Me)-C-i, C6Me6) react in water with 2,4,6-tris(pyridinyl)-1,3,5-triazine (tpt) derivatives in the presence of AgO3SCF3 to form hexanuclear cations of the general formula [Ru-6(eta(6)-arene)(6)(mu(3)-tpt-kappa N)(2)(mu-Cl)(6)](6+). In the presence of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine (4-tpt) the prismatic cations [Ru-6(eta(6)-p-(PrC6H4Me)-C-i)(6)(mu(3)-4-tpt-kappa N)(2)(mu-Cl)(6)](6+) (3) and [Ru-6(eta(6)-C6Me6)(6)(mu(3)-4-tpt-kappa N)(2)(mu-Cl)(6)](6+) (4) have been isolated as the triflate salts, whereas with 2,4,6-tris(pyridin-3-yl)-1,3,5-triazine (3-tpt) [Ru-6(eta(6)-p-(PrC6H4Me)-C-i)(6)(mu(3)-3-tpt-kappa N)(2)(mu-Cl)(6)](6+) (7) and [Ru-6(eta(6)-C6Me6)(6)(mu(3)-3-tpt-kappa N)(2)(mu-Cl)(6)](6+) (8) have been obtained and isolated as the triflate salts. In all cases, the neutral intermediates initially formed prior to the addition of silver triflate have been isolated and characterized as well: [Ru-3(eta(6)-p-(PrC6H4Me)-C-i)(3)(mu(3)-4-tpt-kappa N)Cl-6] (1), [Ru-3(eta(6)-C6Me6)(3)(mu(3)-4-tpt-kappa N)Cl-6] (2), [Ru-3(eta(6)-p-(PrC6H4Me)-C-i)(3)(mu(3)-3-tpt-kappa N)Cl-6] (5), and [Ru-3(eta(6)-C6Me6)(3)(mu(3)-3-tpt-kappa N)Cl-6] (6), respectively. In the case of a trigonal-prismatic hexacation containing p-cymene and 3-tpt ligands, the NMR spectra reveal a mixture of the two isomers 7a and 7b, the formation of which can be rationalized by molecular modeling. The single-crystal structure analyses of [Ru-6(eta(6)-p-(PrC6H4Me)-C-i)(6)(mu(3)-4-tpt-kappa N)(2)(mu-Cl)(6)][O3SCF3](6) ([3][O3SCF3](6)), [Ru-6(eta(6)-C6Me6)(6)(mu(3)-4-tpt-kappa N)(2)(mu-Cl)(6)][O3SCF3](6) ([4][O3SCF3](6)), and [Ru-6(eta(6)-C6Me6)(6)(mu(3)-3-tpt-kappa N)(2)(mu-Cl)(6)][O3SCF3](6) ([8][O3SCF3](6)) reveal strong pi stacking interactions between the two tpt subunits of the trigonal prisms.