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Metal-metal and carbon-carbon bonds as potential components of molecular batteries

机译：金属-金属和碳-碳键作为分子电池的潜在成分

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The reductive coupling of [M(salophen)] derivatives, where M is an early transition metal and salophen is N,N'-o-phenylenebis (salicylideneaminato) dianion, led to the formation of dimers linked through C-C and M-M bonds. Both of these bonds can potentially function as electron reservoirs: each bond can be used as a reversible source of a pair of electrons under the condition that it is not chemically transformed by the incoming substrate which functions as an electron acceptor. To explore this potential function as well as the competition in the redox processes between C-C and M-M bonds within the same molecular framework, we investigated the reduction of [(tBu(4)-salophen)NbCl3] (1) and [(tBu(4)-salophen)MoCl2] (7) as model compounds. In the former case, the reduction led to [(Nb-Nb)(tBu(4)-*salophen(2)*)] (2) which contains both a Nb-Nb bond (2.6525(7) Angstrom) and two C-C bonds across two imino groups of the ligand. Complex 2 can be reduced further to a transient compound 5 that contains an Nb=Nb bond. In the second case, the reduction of 7 by two electrons led to [(Mo drop Mo)(tBu(4)-salophen)(2)] (8), which does not contain any C-C linkages between the two salophen units. Complexes 2 and 5 are able to transfer one pair and two pairs of electrons, respectively, to give compounds 3, 4, and 6, with the consequent cleavage of the Nb-Nb and Nb=Nb bonds. In the present case, it is surprising that the C-C bonds do not participate in the reduction of the substrates. A careful theoretical treatment anticipates, both in the case of 1 and 7 the preferential formation of metal-metal bonds upon reduction. This is indeed the case for 7 but not for 1, where the formation of C-C bonds competes with that of M-M bonds, the latter being the first ones, however, to be involved in electron-transfer reactions. The theoretical approach allowed us to investigate the possibility of intramolecular electron transfer: from C-C bonds to M-M bonds and vice versa. [References: 52]
机译：[M（salophen）]衍生物的还原偶联，其中M为早期过渡金属，而Salophen为N，N'-o-亚苯基双（水杨酰亚氨基）二价阴离子，导致形成通过C-C和M-M键连接的二聚体。这两个键都可能充当电子存储库：每个键都可以用作一对电子的可逆源，条件是它不会被用作电子受体的传入基质化学转化。要探索此潜在功能以及同一分子框架内CC和MM键之间的氧化还原过程中的竞争，我们研究了[（tBu（4）-salophen）NbCl3]（1）和[（tBu（4 ）-salophen）MoCl2]（7）作为模型化合物。在前一种情况下，还原导致[（Nb-Nb）（tBu（4）-* salophen（2）*）]（2）包含Nb-Nb键（2.6525（7）埃）和两个CC跨配体的两个亚氨基键合。配合物2可以进一步还原为包含Nb ＝ Nb键的过渡化合物5。在第二种情况下，两个电子将7还原导致[[Mo降Mo] [tBu（4）-salophen] [2]]（8），该化合物在两个salophen单元之间不包含任何C-C键。配合物2和5能够分别转移一对电子和两对电子，从而生成化合物3、4和6，从而裂解Nb-Nb和Nb = Nb键。在当前情况下，令人惊奇的是，C-C键不参与底物的还原。在1和7的情况下，均会进行认真的理论处理，以期在还原时优先形成金属-金属键。对于7个确实如此，但对于1个却不是，其中C-C键的形成与M-M键的形成竞争，而M-M键是第一个参与电子转移反应的键。理论方法使我们能够研究分子内电子转移的可能性：从C-C键到M-M键，反之亦然。 [参考：52]

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