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首页> 外文期刊>Chemistry: A European journal >Bisguanidines with biphenyl, binaphthyl, and bipyridyl cores: Proton-sponge properties and coordination chemistry
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Bisguanidines with biphenyl, binaphthyl, and bipyridyl cores: Proton-sponge properties and coordination chemistry

机译：具有联苯，联萘和联吡啶核心的双胍：质子海绵性质和配位化学

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摘要

Herein, we report on the synthesis, protonation, and coordination chemistry of chelating guanidine ligands with biphenyl, binaphthyl, and bipyridyl backbones. The ligands are shown to be proton sponges, and this protonation was studied experimentally and by using quantum-chemical calculations. Group 10 metal (Ni, Pd, and Pt) complexes with different metal/ligand ratios were synthesized. In the case of the bipyridyl systems, coordination occurs exclusively at the pyridine N atoms, as opposed to protonation. The spin-density distribution and the magnetism were evaluated for a series of paramagnetic Ni~(II) complexes with the aid of paramagnetic NMR spectroscopic studies in alliance with quantum-chemical calculations and magnetic (SQUID) measurements. Through direct delocalization from the singly occupied molecular orbitals (SOMOs), a significant amount of spin density is placed on the guanidinyl groups, and spin polarization also transports spin density onto the aromatic backbone. Showing some backbone: Bisguanidines with flexible biaryl backbones are proton sponges and ligands in a series of new mono- and dinuclear Group 10 metal complexes (see figure). The spin-density distribution in paramagnetic Ni~(II) complexes was studied by using NMR spectroscopy and quantum-chemical calculations.
机译：在此，我们报道了具有联苯，联萘和联吡啶骨架的螯合胍配体的合成，质子化和配位化学。配体显示为质子海绵，并且通过实验和使用量子化学计算研究了该质子化。合成了具有不同金属/配体比率的第10组金属（Ni，Pd和Pt）配合物。在联吡啶系统的情况下，与质子化相反，配位仅在吡啶的N原子上发生。借助顺磁性NMR光谱研究结合量子化学计算和磁性（SQUID）测量，对一系列顺磁性Ni〜（II）配合物的自旋密度分布和磁性进行了评估。通过直接从单个占据的分子轨道（SOMO）进行离域，将大量自旋密度置于胍基上，并且自旋极化还将自旋密度传输到芳族骨架上。显示一些主链：具有柔性联芳基主链的双胍是质子海绵和一系列新的单核和双核第10组金属配合物中的配体（见图）。利用NMR光谱和量子化学计算研究了顺磁性Ni〜（II）配合物的自旋密度分布。

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