双原子一氟化硼与铁的末端配位,Science

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双原子一氟化硼与铁的末端配位
Science ( IF 44.7 ) Pub Date : 2019-03-14 , DOI: 10.1126/science.aaw6102
Myles J. Drance ₁ , Jeffrey D. Sears ₂ , Anthony M. Mrse ₁ , Curtis E. Moore ₁ , Arnold L. Rheingold ₁ , Michael L. Neidig ₂ , Joshua S. Figueroa ₁

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铁的新最佳朋友一氧化碳 (CO) 是过渡金属化学中研究最广泛的配体之一。其显着特征之一是双向键合基序，其中 CO 向金属提供电子，而金属同时在另一个方向进行“反向键合”。理论表明等电子氟化硼双原子 BF 对两种类型的键合甚至更有效。然而，制备用于比较的必需化合物一直具有挑战性。德兰斯等人。现在报告合成了末端铁-BF 复合物，其供体和受体特征与类似的 CO 和 N2 复合物相比具有优势。科学，这个问题 p。1203 与一氧化碳等电子的氟化硼配体以类似但更强的方式与铁结合。一氟化硼 (BF) 是一种双原子分子，具有 10 个价电子，与一氧化碳 (CO) 等电子。与 CO 不同，CO 在室温下是一种稳定的分子，并且很容易充当过渡金属的桥接和末端配体，而 BF 在气相中低于 1800°C 时不稳定，并且其配位化学受到很大限制。在这里，我们报告了铁络合物 Fe(BF)(CO)2(CNArTripp2)2 [ArTripp2, 2,6-(2,4,6-(i-Pr)3C6H2]2C6H3; i-Pr, iso -丙基]，具有末端 BF 配体。单晶 X 射线衍射以及核磁共振、红外、Fe(BF)(CO)2(CNArTripp2)2 和等电子二氮 (N2) 和 CO 配合物 Fe(N2)(CO)2(CNArTripp2)2 和 Fe(CO)3(CNArTripp2)2 的穆斯堡尔光谱研究表明BF 末端配体具有特别强的 σ-供体和 π-受体特性。密度泛函理论和电子密度拓扑计算支持这一结论。

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Terminal coordination of diatomic boron monofluoride to iron

Iron's new Best Friend Carbon monoxide (CO) is one of the most widely studied ligands in the chemistry of transition metals. One of its distinguishing features is a two-way bonding motif, in which CO donates electrons to the metal while the metal simultaneously engages in “back bonding” in the other direction. Theory has suggested that the isoelectronic boron fluoride diatomic, BF, would be even more effective at both types of bonding. However, it has been challenging to prepare the requisite compounds for comparison. Drance et al. now report synthesis of a terminal iron-BF complex, with donor and acceptor characteristics that compare favorably to analogous CO and N2 complexes. Science, this issue p. 1203 A boron fluoride ligand isoelectronic with carbon monoxide binds to iron in similar but stronger fashion. Boron monofluoride (BF) is a diatomic molecule with 10 valence electrons, isoelectronic to carbon monoxide (CO). Unlike CO, which is a stable molecule at room temperature and readily serves as both a bridging and terminal ligand to transition metals, BF is unstable below 1800°C in the gas phase, and its coordination chemistry is substantially limited. Here, we report the isolation of the iron complex Fe(BF)(CO)2(CNArTripp2)2 [ArTripp2, 2,6-(2,4,6-(i-Pr)3C6H2]2C6H3; i-Pr, iso-propyl], featuring a terminal BF ligand. Single-crystal x-ray diffraction as well as nuclear magnetic resonance, infrared, and Mössbauer spectroscopic studies on Fe(BF)(CO)2(CNArTripp2)2 and the isoelectronic dinitrogen (N2) and CO complexes Fe(N2)(CO)2(CNArTripp2)2 and Fe(CO)3(CNArTripp2)2 demonstrate that the terminal BF ligand possesses particularly strong σ-donor and π-acceptor properties. Density functional theory and electron-density topology calculations support this conclusion.

更新日期：2019-03-14

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