Detailed evaluation of the geometric and electronic structures of one-electron oxidized group 10 (Ni, Pd, and Pt) metal(II)-(disalicylidene)diamine complexes.
Detailed evaluation of the geometric and electronic structures of one-electron oxidized group 10 (Ni, Pd, and Pt) metal(II)-(disalicylidene)diamine complexes.
复制标题
单电子氧化第 10 族（Ni、Pd 和 Pt）金属 (II)-(二水杨基)二胺配合物的几何和电子结构的详细评估。
DOI：
10.1021/ic901003q
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发表时间：
2009
影响因子：
4.6
通讯作者：
Storr,Tim
中科院分区：
文献类型：
--
作者：
Shimazaki,Yuichi;Stack,TDanielP;Storr,Tim
研究了一系列单电子氧化的第10族金属化合物(Ni、Pd、Pt)在溶液和固态中的几何结构和电子结构。研究了四齿Salen配体N，N′-bis(3，5-di-tert-butylsalicylidene)-1，2-cyclohexanediamine(H_2Salcn)的Ni(1)和Pd(2)配合物以及Salen配体N，N′-bis(3，5-di-tert-butylsalicylidene)-1，2-ethylenediamine(H_2Salen)的铂(3)配合物。这三种氧化化合物在溶液和固体中都以配体自由基物种的形式存在。[1]+和[3]+的固态结构相对于中性结构呈现对称的配位球收缩。相比之下，Pd衍生物[2]+的配位球在固态下表现出明显的不对称性。在溶液中，被氧化的衍生物表现出强烈的低能NIR跃迁，这与它们被归类为配体自由基化合物是一致的。有趣的是，在镍、钯和铂系列中，酚类部分之间的通讯程度强烈地依赖于中心金属离子。电化学测量和UV−Vis−近红外光谱，结合密度泛函理论计算，提供了对这些系统中单电子空穴离域程度的见解。Pd络合物[2]+是离域最少的，根据Robin−Day分类系统，最好将其描述为边界的II/III类价态络合物。镍[1]+和铂[3]+类似物是第III类(完全离域)价间化合物。离域依赖于氧化还原活性的酚类配体之间的电子耦合，这种耦合是由正式填充的金属dxz轨道和适当的配体分子轨道之间的重叠所介导的。对于单电子氧化的第10族金属SALENS，偶合度按Pd<；Ni<；Pt的顺序增加。
The geometric and electronic structures of a series of one-electron oxidized group 10 metal salens (Ni, Pd, Pt) have been investigated in solution and in the solid state. Ni (1) and Pd (2) complexes of the tetradentate salen ligandN,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (H2Salcn) have been examined along with the Pt (3) complex of the salen ligandN,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediamine (H2Salen). All three oxidized compounds exist as ligand radical species in solution and in the solid state. The solid state structures of [1]+and [3]+exhibit a symmetric coordination sphere contraction relative to the neutral forms. By contrast, the coordination sphere of the Pd derivative [2]+exhibits a pronounced asymmetry in the solid state. In solution, the oxidized derivatives display intense low-energy NIR transitions consistent with their classification as ligand radical compounds. Interestingly, the degree of communication between the phenolate moieties depends strongly on the central metal ion, within the Ni, Pd, and Pt series. Electrochemical measurements and UV−vis−NIR spectroscopy, in conjunction with density functional theory calculations provide insights into the degree of delocalization of the one-electron hole in these systems. The Pd complex [2]+is the least delocalized and is best described as a borderline Class II/III intervalence complex based on the Robin−Day classification system. The Ni [1]+and Pt [3]+analogues are Class III (fully delocalized) intervalence compounds. Delocalization is dependent on the electronic coupling between the redox-active phenolate ligands, mediated by overlap between the formally filled metal dxzorbital and the appropriate ligand molecular orbital. The degree of coupling increases in the order Pd < Ni < Pt for the one-electron oxidized group 10 metal salens.