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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Electronic structure predictions of the properties of non-innocent P-ligands in group 6B transition metal complexes
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Electronic structure predictions of the properties of non-innocent P-ligands in group 6B transition metal complexes

机译：6B族过渡金属配合物中非纯P-配体性质的电子结构预测

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摘要

Neutral group 6B (Cr, Mo, W) pentacarbonyl complexes M(CO)_5-L possessing various P-ligands such as phosphines, phosphaalkenes, and phospha-quinomethanes can form radical cations and anions under redox conditions. There is significant interest in whether the radical site is localized on the metal or on a "non-innocent" ligand. Density functional theory was used to predict whether the radicals of the complexes behave as metal or ligand-centered radicals and whether these compounds could form in solution or as an ion pair with various oxidizing and reducing agents. The quinone-like ligands are predicted to be ligand centered radicals when they are anions and metal centered radicals when they are cations. The predicted reaction energies for single electron transfer (SET) reactions involving the quinone like ligands are negative or near thermoneutral for both radicals in polar solutions and as solid state ion pairs. The energetics of the SET reactions can be controlled by the nature of L, the nature of the oxidizing/reducing agent, and the solvent polarity. Such complexes could be used as flexible catalysts for single electron transfer reactions.
机译：具有各种P-配体例如膦，磷烯和磷-喹甲烷的中性基团6B（Cr，Mo，W）五羰基配合物M（CO）_5-L可以在氧化还原条件下形成自由基阳离子和阴离子。人们对自由基位点是位于金属上还是位于“非纯”配体上有着极大的兴趣。密度泛函理论用于预测络合物的自由基是否表现为金属或配体中心的自由基，以及这些化合物是否可以在溶液中形成或与各种氧化剂和还原剂形成离子对。醌类配体当它们为阴离子时被预测为以配体为中心的自由基，而当它们为阳离子时其被视为以金属为中心的自由基。对于极性溶液中的两个自由基以及作为固态离子对，涉及醌类配体的单电子转移（SET）反应的预测反应能量均为负或接近热中性。 SET反应的能量可以通过L的性质，氧化剂/还原剂的性质和溶剂极性来控制。此类络合物可用作单电子转移反应的柔性催化剂。

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