Allred Russell A, McAlexander Lenore H, Arif Atta M, Berreau Lisa M
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, USA.
Inorg Chem. 2002 Dec 16;41(25):6790-801. doi: 10.1021/ic0258072.
Treatment of the bmnpa (N,N-bis-2-(methylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine) ligand with equimolar amounts of Cd(ClO(4))(2).5H(2)O and Me(4)NOH.5H(2)O in CH(3)CN yielded the binuclear cadmium hydroxide complex ((bmnpa)Cd)(2)(mu-OH)(2)(2).CH(3)CN (1). Complex 1 may also be prepared (a) by treatment of a CH(3)CN solution of (bmnpa)Cd(ClO(4))(2) (2) with 1 equiv of n-BuLi, followed by treatment with water or (b) from 2 in the presence of 1 equiv each of water and NEt(3). The hydroxide derivative 1 is not produced from 2 and water in the absence of an added base. Complex 1 possesses a binuclear structure in the solid state with hydrogen-bonding and CH/pi interactions involving the bmnpa ligand. The overall structural features of 1 differ from the halide derivative ((bmnpa)Cd)(2)(mu-Cl)(2)(2) (3), particularly in that the Cd(2)(mu-OH)(2) core of 1 is symmetric whereas the Cd(2)(mu-Cl)(2) core of 3 is asymmetric. In acetonitrile solution, 1 behaves as a 1:2 electrolyte and retains a binuclear structure and secondary hydrogen-bonding and CH/pi interactions, whereas 3 is a 1:1 electrolyte, indicating formation of a mononuclear [(bmnpa)CdCl]ClO(4) species in solution. Treatment of 1 with CO(2) in anhydrous CH(3)CN yields the bridging carbonate complex ((bmnpa)Cd)(2)(mu-CO(3))(2).CH(3)CN (4). Treatment of a chemically similar zinc hydroxide complex, ((benpa)Zn)(2)(mu-OH)(2)(2) (benpa = N,N-bis-2-(ethylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine, with CO(2) also results in the formation of a carbonate derivative, ((benpa)Zn)(2)(mu-CO(3))(2) (5), albeit the coordination mode of the bridging carbonate moiety is different. Treatment of 4 with added water results in no reaction, whereas 5 under identical conditions will undergo reaction to yield the zinc hydroxide complex ((benpa)Zn)(2)(mu-OH)(2)(2).
在乙腈中，将bmnpa（N，N-双-2-（甲硫基）乙基-N-（（6-新戊基氨基-2-吡啶基）甲基）胺）配体与等摩尔量的Cd(ClO₄)₂·5H₂O和Me₄NOH·5H₂O反应，得到双核氢氧化镉配合物((bmnpa)Cd)₂(μ-OH)₂₂·CH₃CN (1)。配合物1也可以通过以下方法制备：(a) 用1当量的正丁基锂处理(bmnpa)Cd(ClO₄)₂ (2)的乙腈溶液，然后用水处理；或者(b) 在水和三乙胺各1当量存在的情况下由2制备。在没有添加碱的情况下，2和水不会生成氢氧化物衍生物1。配合物1在固态时具有双核结构，涉及bmnpa配体的氢键和CH/π相互作用。1的整体结构特征与卤化物衍生物((bmnpa)Cd)₂(μ-Cl)₂₂ (3)不同，特别是1的Cd₂(μ-OH)₂核心是对称的，而3的Cd₂(μ-Cl)₂核心是不对称的。在乙腈溶液中，1表现为1:2电解质，并保留双核结构以及二级氢键和CH/π相互作用，而3是1:1电解质，表明在溶液中形成了单核[(bmnpa)CdCl]ClO₄物种。在无水乙腈中用CO₂处理1得到桥连碳酸根配合物((bmnpa)Cd)₂(μ-CO₃)₂·CH₃CN (4)。用CO₂处理化学性质相似的氢氧化锌配合物((benpa)Zn)₂(μ-OH)₂₂（benpa = N，N-双-2-（乙硫基）乙基-N-（（6-新戊基氨基-2-吡啶基）甲基）胺）也会形成碳酸酯衍生物((benpa)Zn)₂(μ-CO₃)₂ (5)，尽管桥连碳酸根部分的配位模式不同。用添加的水处理4不发生反应，而在相同条件下5会发生反应生成氢氧化锌配合物((benpa)Zn)₂(μ-OH)₂₂。
