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Intramolecular Associative and Dissociative Electron-Transfer Reactions of Rhodium Complexes

机译：铑配合物的分子内联合和解离电子转移反应

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摘要

Reversible formation and cleavage of Rh-N bonds are observed in anodic electron-transfer reactions of complexes of the type RhLL'(Tp'), where Tp' is the hydrotris(3,5-dimethylpyrazolyl)borate anion. Two pyrazolyl rings are coordinated to Rh in the neutral complex and three rings are coordinated in the monocations when at least L or L' is a bulky two-electron ligand such as triphenylphosphine. The overall redox process is then a square scheme with rate-limiting electron transfer. With less bulky ligands (e.g. phosphates) a quasi-nernstian electron-transfer process is observed. Detailed mechanistic treatments, including homogeneous redox catalysis measurements, support a sequence of chemically reversible EC two-step processes when LL' = (PPh _3)_2 or (CO)(PCy_3) (Cy = cyclohexadienyl) but single-step E processes are seen when LL' = (CO)(P(OMe)_3) or (CO)(P(OPh)_3. The implications of these findings will be discussed in terms of concerted vs consecutive intramolecular bond cleavage electron-transfer reactions.
机译：在RHL'（TP'）的复合物的阳极电子转移反应中观察到Rh-N键的可逆形成和切割，其中TP'是水溶式（3,5-二甲基吡唑基）硼酸盐阴离子。在中性复合物中与Rh配位两种吡唑基环，当至少L或L'是诸如三苯基膦的庞大的双电子配体时，在单体中配位三个环。然后整体氧化还原过程是具有速率限制电子转移的正方形方案。具有较少的庞大的配体（例如磷酸盐），观察到准无钻头电子转移过程。当LL'=（PPH _3）_2或（CO）（PCY_3）（CY =环己二烯基）但单步E过程中，载体提供均匀的氧化还原催化测量，包括均匀氧化还原催化测量，支持一系列化学可逆的EC两步处理。当ll'=（co）（p（ome）_3）或（co）（p（oph）_3时。将根据齐全的与连续分子内键切割电子转移反应来讨论这些发现的影响。

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