Chromium and Molybdenum Carbonyl Derivatives of N2O2 Schiff Base and 2(2'-Pyridyl) Benzimidazole

R. Ramadan, O. Ali, A. S. Sayed
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Abstract

The chemistry of Schiff bases is an area of increasing interest. Importance of these bases and their metal complexes is retained to their applications in biological, analytical and industrial fields as well as to their roles in catalysis and organic synthesis [1–9]. On the other hand, transition metal complexes having oxygen and nitrogen donor Schiff bases mostly possess unusual configuration, structural lability and are sensitive to molecular environment [10]. For example, the environment around the metal centre (such as coordination geometry, number of coordinated ligands and their donor groups) is the key factor for metalloproteins to carry out specific physiological functions [11]. The design and synthesis of symmetrical Schiff bases have been of interest due to their preparative accessibility, structural variability and tunable electronic properties allowing carrying out systematic reactivity studies based on ancillary ligand modifications [12]. Moreover, Schiff base ligands that are able to form binuclear transition metal complexes are useful to study the relation between structures and magnetic exchange interactions [13,14]. In addition, transition metal complexes with tetradentate Schiff bases have been extensively investigated as catalysts for a number of organic redox reactions and electrochemical reduction processes [15-17]. The chemistry of metal complexes containing salen-type (N2O2) Schiff base ligands derived from condensation of aldehydes and diamines are of enduring significance. These complexes have been used as synthetic oxygen carriers [18], catalysts for the asymmetric epoxidation [19-24] and the synthesis of optical and magnetic materials [25,26]. Salen complexes have also been recently used as catalytically active materials to develop surface-modified electrodes for sensoring applications [27,28]. On the other hand, transition metal complexes with 2-substituted benzimidazole ligands are progressively used to model important bioinorganic systems [29,30] and act as cytotoxic [31], antiviral [32] and antiamoebic [33] agents. Our interest in investigation of the reactions of metal carbonyls with Schiff bases [34-39] has prompted us to investigate the reactions of M(CO)6 (M=Cr or Mo) with bis(salicylaldehyde) ethylendiimine (salenH2) in presence of 2(2'-pyridyl) benzimidazole (PbiH) (Scheme 1).
N2O2席夫碱和2(2′-吡啶基)苯并咪唑的铬钼羰基衍生物
希夫碱的化学性质是一个日益引起人们兴趣的领域。这些碱及其金属配合物的重要性在于它们在生物、分析和工业领域的应用,以及它们在催化和有机合成中的作用[1-9]。另一方面,具有氧和氮施主席夫碱的过渡金属配合物大多具有特殊的构型、结构稳定性和对分子环境的敏感性。例如,金属中心周围的环境(如配位几何、配位配体及其供体基团的数量)是金属蛋白执行特定生理功能的关键因素[11]。对称席夫碱的设计和合成由于其制备的可及性、结构的可变性和可调的电子性质而引起了人们的兴趣,这使得基于辅助配体修饰[12]的系统反应性研究成为可能。此外,能够形成双核过渡金属配合物的希夫碱配体有助于研究结构与磁交换相互作用之间的关系[13,14]。此外,具有四齿席夫碱的过渡金属配合物作为多种有机氧化还原反应和电化学还原过程的催化剂已被广泛研究[15-17]。由醛和二胺缩合而成的含salen型(N2O2)希夫碱配体的金属配合物的化学性质具有持久的意义。这些配合物已被用作合成氧载体[18]、不对称环氧化催化剂[19-24]以及光学和磁性材料的合成[25,26]。Salen配合物最近也被用作催化活性材料,用于开发用于传感应用的表面修饰电极[27,28]。另一方面,具有2-取代苯并咪唑配体的过渡金属配合物逐渐被用于模拟重要的生物无机系统[29,30],并作为细胞毒性[31]、抗病毒[32]和抗阿米巴药物[33]。我们对研究金属羰基与希夫碱的反应感兴趣[34-39],这促使我们研究了M(CO)6 (M=Cr或Mo)与双(水杨醛)乙基二亚胺(salenH2)在2(2'-吡啶基)苯并咪唑(PbiH)存在下的反应(方案1)。
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