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首页> 外文期刊>Chemistry: A European journal >The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry
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The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry

机译：三核镓桥联的二茂铁oph烷[{Fe（eta（5）-C5H4）（2）}（3）Ga-2]：合成，键合，结构和配位化学

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摘要

The trinuclear ferrocenophane [{Fe(eta(5)-C5H4)(3)}(2)Ga-2] (3) featuring two sp(2)-hybridized gallium atoms in bridging positions between three ferrocene-1,1'-diyl units represents a novel type of ferrocene derivative. Compound 3 is obtained by thermal treatment of 1,1'-bis(dimethylgallyl)ferrocene (1) in nondonor solvents or in diethyl ether as solvent and subsequent thermal decomplexation. The [1.1]ferrocenophane [{Fe(eta(5)-C5H4)(2)}(2){GaMe}(2)] (2) is an intermediate in the formation of 3. The reaction of 3 with an excess of trimethylgallium leads back to 1 and proves the reversibility of the multistep reaction sequence. Theoretical calculations reveal a carousel-type D-3h structure for 3. The compound can best be described as being composed of three only weakly interacting ferrocenediyl units covalently connected by gallium atoms without any pi-bond contribution in the Ga-C bonds. Owing to steric constraints 3 cannot be reduced to the dianion 3(2-), which would feature a Ga-Ga bond. Compound 3 represents a stereochemically rigid difunctional Lewis acid allowing the formation of the adducts 3a-3d possessing linear donor-aceptor-aceptor-donor arrangements. Crystal structure data for 3a-3d show a symmetry-reduced chiral ferrocenophane core (D-3h -> D-3). A polymeric rodlike structure is observed for 3b and 3d caused by it-stacking effects (3b) or by a difunctional donor-acceptor interaction (3d). In solution, the chirality of the adducts is lost by rapid interconversion of the enantiomers. A cyclic voltammogram of 3b in pyridine reveals three quasi-reversible oxidation steps at -356, -154, and 8 mV, indicating only weak electron delocalization in the cationic species. The redox potentials of the pyridine adduct 3b are compared with those of other pyridine-stabilized gallyl-sustituted ferrocene derivatives and with ferrocene itself.
机译：三核二茂铁[[Fe（eta（5）-C5H4）（3）}（2）Ga-2]（3）在三个二茂铁-1,1'-之间的桥连位置具有两个sp（2）杂化的镓原子二基单元代表一种新型的二茂铁衍生物。通过在非供体溶剂或在作为溶剂的二乙醚中热处理1,1'-双（二甲基烯丙基）二茂铁（1），然后进行热分解，可以得到化合物3。 [1.1]二茂铁oph烷[{Fe（eta（5）-C5H4）（2）}（2）{GaMe}（2）]（2）是形成3的中间体。3与过量的3三甲基镓返回到1并证明了多步反应序列的可逆性。理论计算揭示了3的旋转木马型D-3h结构。该化合物可以最好地描述为由镓原子共价连接的三个仅有的弱相互作用的二茂铁二烯单元组成，在Ga-C键中没有任何pi键。由于空间约束3，不能将其还原为具有Ga-Ga键的二价阴离子3（2-）。化合物3代表立体化学刚性的双官能路易斯酸，其允许形成具有线性供体-受体-受体-供体排列的加合物3a-3d。 3a-3d的晶体结构数据显示出对称性降低的手性二茂铁玻璃芯（D-3h-> D-3）。对于3b和3d，观察到了聚合的棒状结构，这是由于其堆积效应（3b）或双功能供体-受体相互作用（3d）引起的。在溶液中，对映异构体的快速相互转化丧失了加合物的手性。吡啶中3b的循环伏安图显示-356，-154和8 mV处三个准可逆的氧化步骤，表明在阳离子物种中仅弱的电子离域作用。将吡啶加合物3b的氧化还原电势与其他吡啶稳定的没食子基化的二茂铁衍生物的氧化还原电势以及与二茂铁本身进行比较。

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