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钯（二异丙基膦钯）：立方晶系，不饱和，零价。

Pd(PDip): Cubic, Unsaturated, Zerovalent.

作者信息

Breitwieser Kevin, Bevilacqua Matteo, Mullassery Sneha, Dankert Fabian, Morgenstern Bernd, Grandthyll Samuel, Müller Frank, Biffis Andrea, Hering-Junghans Christian, Munz Dominik

机构信息

Coordination Chemistry Saarland University, Campus C4.1, D-66123, Saarbrücken, Germany.

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, Padova, I-35131, Italy.

出版信息

Adv Sci (Weinh). 2024 Jul;11(25):e2400699. doi: 10.1002/advs.202400699. Epub 2024 Apr 18.

DOI:10.1002/advs.202400699
PMID:38634573
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11220702/
Abstract

Atomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic- as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd(PDip) that is fully characterized by mass spectrometry, heteronuclear and Cross-Polarization Magic-Angle Spinning (CP-MAS) NMR-, infrared (IR), UV-vis, and X-ray photoelectron (XP) spectroscopies, single-crystal X-Ray diffraction (sc-XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104-electron Pd(0) cluster features a cubic Pd-core, µ-capping phosphinidene ligands, and is air-stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non-destructive cluster rearrangement as is required for supramolecular assembly.

摘要

原子精确的纳米团簇在超分子组装以及（光）电子和磁性材料方面具有应用前景。在此，本工作报道用三磷杂环丙烷处理零价钯前体可得到颜色强烈的Pd(PDip)，通过质谱、异核和交叉极化魔角旋转（CP-MAS）核磁共振、红外（IR）、紫外可见和X射线光电子（XP）光谱、单晶X射线衍射（sc-XRD）、质谱和循环伏安法（CV）对其进行了全面表征。这种配位不饱和的104电子零价钯团簇具有立方钯核、μ-盖帽亚膦基配体，并且在空气中稳定。量子化学计算深入了解了团簇的电子结构，并表明存在5s/4d轨道混合以及轻微的钯-磷共价性。捕获实验表明团簇的生长是通过零价钯插入三磷杂环丙烷进行的。不饱和团簇能感知乙烯并与异腈结合，这会引发重排为具有减小的前沿轨道能隙的四面体结构。这些实验证明了团簇操作简便，并突出了超分子组装所需的非破坏性团簇重排。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/931f9be930fe/ADVS-11-2400699-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/9214d2ca28bd/ADVS-11-2400699-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/4d27cb3252f4/ADVS-11-2400699-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/540b3d76a0f4/ADVS-11-2400699-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/9194d8de5664/ADVS-11-2400699-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/0b19d74561d8/ADVS-11-2400699-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/372cb2c143e5/ADVS-11-2400699-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/931f9be930fe/ADVS-11-2400699-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/9214d2ca28bd/ADVS-11-2400699-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/4d27cb3252f4/ADVS-11-2400699-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/540b3d76a0f4/ADVS-11-2400699-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/9194d8de5664/ADVS-11-2400699-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/0b19d74561d8/ADVS-11-2400699-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/372cb2c143e5/ADVS-11-2400699-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f68f/11220702/931f9be930fe/ADVS-11-2400699-g002.jpg

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