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首页> 外文期刊>Chemistry: A European journal >Electronic Structures of Five-Coordinate Complexes of Iron Containing Zero, One, or Two pi-Radical Ligands: A Broken-Symmetry Density Functional Theoretical Study
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Electronic Structures of Five-Coordinate Complexes of Iron Containing Zero, One, or Two pi-Radical Ligands: A Broken-Symmetry Density Functional Theoretical Study

机译：含零，一或两个π径向配体的铁的五坐标络合物的电子结构：对称对称破缺的泛函理论研究

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The electronic structures of a series of five-coordinate complexes of iron containing zero, one, or two biden-tate, organic pi-radical ligands and a monodentate ligand (pyridine, iodide) have been studied by broken-symmetry (BS) density functional theoretical (DFT) methods. By analyzing the set of corresponding orbitals (CO) a convenient division of the spin-up and spin-down orbitals into 1) essentially doubly-occupied molecular orbitals (MO), 2) exactly singly-occupied MOs, 3) spin-coupled pairs, and 4) virtual orbitals can be achieved and a clear picture of the spin coupling between theligands (non-innocence vs. innocence) and the central metal ion (d~N configuration) can be generated. We have identified three classes of complexes which all contain a ferric ion (d~5) with an intrinsic intermediate spin (S_(Fe) = 3/2) that yield 1) an S_t = 3/2 ground spin state if the two bidentate ligands are closed-shell species (innocent ligands); 2) if one pi-radical ligand is present, an S_t = 1 ground state is ob-tained through intramolecular antifer-romagnetic coupling; 3) if two such radicals are present, an S_t = 1/2 ground state is obtained. We show unambiguously for the first time that the pen-tane-2,4-dione-bis(S-alkylisothiosemi-carbazonato) ligand can bind as pi-radi-cal dianion (L_(TSC)~(centre dot))~(2-) in [Fe~(III)(L_(TSC)~(centre dot))I] (S_t = 1) (6); the description as [Fe~(IV)-(L_(TSC)~(3-))I] is incorrect. Similarly, the diamagnetic monoanion in 14 must be described as [Fe~(III)(CN)_2(L_(TSC)~(centre dot))]~- (S_t = 0) with a low-spin ferric ion (d~5, S_(Fe) = 1/2) coupled antiferromagnetically to a pi-radical ligand; [Fe~(II)(CN)_2(L_(TSC)~-)]~- is an incorrect description.
机译：通过断裂对称（BS）密度泛函研究了含五个，六个或两个双齿有机π-自由基配体和一个单齿配体（吡啶，碘化物）的铁的五配位配合物的电子结构。理论（DFT）方法。通过分析相应的轨道（CO）的集合，可以方便地将自旋向上和向下旋转的轨道分为1）本质上是双重占据的分子轨道（MO），2）完全是单个占据的MOs，3）自旋耦合对，以及4）可以实现虚拟轨道，并且可以清晰地看到配体（无毒与无毒）与中心金属离子（d〜N构型）之间的自旋耦合。我们已经确定了三类络合物，它们都包含具有固有中间自旋（S_（Fe）= 3/2）的三价铁离子（d〜5），如果两个二齿是三价复合物，则产生1）S_t = 3/2基态自旋配体是闭壳物种（无害配体）; 2）如果存在一个π-自由基配体，则通过分子内反铁磁耦合获得S_t = 1基态; 3）如果存在两个这样的自由基，则获得S_t = 1/2基态。我们首次明确表明，戊烷-2,4-二酮-双（S-烷基异硫半乳糖-咔唑酮）配体可以作为pi-radi-cal二价阴离子（L_（TSC）〜（中心点））〜（ [Fe〜（III）（L_（TSC）〜（中心点））I]中的2-）（S_t = 1）（6）; [Fe〜（IV）-（L_（TSC）〜（3-））I]的描述不正确。类似地，必须将14中的反磁性单阴离子描述为[Fe〜（III）（CN）_2（L_（TSC）〜（中心点））]〜-（S_t = 0）和低旋铁离子（d〜 5，S_（Fe）= 1/2）反铁磁耦合至π-自由基配体; [Fe〜（II）（CN）_2（L_（TSC）〜-）]〜-是错误的描述。

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