Inorganic clusters as metalloligands: ligand effects on the synthesis and properties of ternary nanopropeller clusters
Inorganic clusters as metalloligands: ligand effects on the synthesis and properties of ternary nanopropeller clusters
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DOI：
10.1039/d0dt02416c
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发表时间：
2020-12-07
影响因子：
4
通讯作者：
Velian, Alexandra
中科院分区：
文献类型：
--
作者：
Kephart, Jonathan A.;Boggiano, Andrew C.;Velian, Alexandra
具有合成可寻址和半不稳定活性位点的氧化还原活性多金属平台是有吸引力的合成靶点，用于模拟酶辅助因子对多电子转化的反应性。为此，一个家庭的三元簇具有三个边缘金属网站锚定在[Co 6Se 8]多金属支持通过氨基膦配体是一个很有前途的平台。在这份报告中，我们探讨了这些配体的立体电子性质的微小变化如何改变[Co 6Se 8]金属配体的形成，而且在两个新的三元簇M3 Co 6Se 8L 6（M = Zn，Fe; L（-）= Ph 2 PN（-）iPr）的边缘/支持相互作用的底物结合亲和力和强度。这些集群的特点是广泛使用一系列的方法，包括单晶X射线衍射，电子吸收光谱和循环伏安法。底物结合研究表明，Fe 3Co 6Se 8L 6抵抗较大配体如吡啶或四氢呋喃的配位，但结合较小配体（CNBu）-Bu-t。此外，对使用两种氨基膦Ph 2 PN（H）Pr 1（L-H）和（Pr 2 PN）-Pr 1（H）Pr 1合成新的[Co 6Se 8]金属配体的研究导致Co 6Se 8L 6 H以及较小的簇Co 4Se 2（CO）（6）L-4（H）、Co 3Se（mu（2）-PPh 2）（CO）（4）L-3（H）、和[Co（CO）（3）（（Pr2PN）-Pr1（H）Pr1）]（2）。累积，这项研究扩大了我们的理解的立体电子性质的氨基膦配体的钴硫族化物簇的合成的效果，重要的是调制之间的推拉动态[Co 6Se 8]支持，边缘金属和传入的配位体在三元M3 Co 6Se 8L 6簇。
Redox-active multimetallic platforms with synthetically addressable and hemilabile active sites are attractive synthetic targets for mimicking the reactivity of enzymatic co-factors toward multielectron transformations. To this end, a family of ternary clusters featuring three edge metal sites anchored on a [Co6Se8] multimetallic support via amidophosphine ligands are a promising platform. In this report, we explore how small changes in the stereoelectronic properties of these ligands alter [Co6Se8] metalloligand formation, but also substrate binding affinity and strength of the edge/support interaction in two new ternary clusters, M3Co6Se8L6 (M = Zn, Fe; L(-) = Ph2PN(-)iPr). These clusters are characterized extensively using a range of methods, including single crystal X-ray diffraction, electronic absorption spectroscopy and cyclic voltammetry. Substrate binding studies reveal that Fe3Co6Se8L6 resists coordination of larger ligands like pyridine or tetrahydrofuran, but binds the smaller ligand (CNBu)-Bu-t. Additionally, investigations into the synthesis of new [Co6Se8] metalloligands using two aminophosphines, Ph2PN(H)Pr-i (L-H) and (Pr2PN)-Pr-i(H)Pr-i, led to the synthesis and characterization of Co6Se8L6H, as well as the smaller clusters Co4Se2(CO)(6)L-4(H), Co3Se(mu(2)-PPh2)(CO)(4)L-3(H), and [Co(CO)(3)((Pr2PN)-Pr-i(H)Pr-i)](2). Cumulatively, this study expands our understanding on the effect of the stereoelectronic properties of aminophosphine ligands in the synthesis of cobalt chalcogenide clusters, and, importantly on modulating the push-pull dynamic between the [Co6Se8] support, the edge metals and incoming coordinating ligands in ternary M3Co6Se8L6 clusters.