Terminal coordination of diatomic boron monofluoride to iron
Terminal coordination of diatomic boron monofluoride to iron
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DOI：
10.1126/science.aaw6102
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发表时间：
2019-03-15
期刊：
影响因子：
56.9
通讯作者：
Figueroa, Joshua S.
中科院分区：
文献类型：
--
作者：
Drance, Myles J.;Sears, Jeffrey D.;Figueroa, Joshua S.
单氟化硼（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。CO在室温下是一种稳定的分子，很容易作为过渡金属的桥接和末端配体，而BF在1800℃以下的气相中是不稳定的，其配位化学性质基本上是有限的。本文报道了铁配合物Fe(BF)(CO)(2)(CNArTripp2)(2) [ar - tripp2,2,6 -(2,4,6-(i-Pr)(3)C6H2](2)C6H3；i-Pr，异丙基]，具有末端BF配体。对Fe(BF)(CO)(2)(CNArTripp2)(2)以及等电子二氮（N-2）和CO配合物Fe(N-2)(CO)(2)(CNArTripp2)(2)和Fe(CO)(3)（CNArTripp2)(2)）的单晶x射线衍射、核磁共振、红外和穆斯堡尔光谱的研究表明，末端BF配体具有特别强的sigma-供体和pi-受体性质。密度泛函理论和电子密度拓扑计算支持这一结论。
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 degrees 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) [Ar-Tripp2, 2,6-(2,4,6-(i-Pr)(3)C6H2](2)C6H3; i-Pr, iso-propyl], featuring a terminal BF ligand. Single-crystal x-ray diffraction as well as nuclearmagnetic resonance, infrared, and Mossbauer spectroscopic studies on Fe(BF)(CO)(2)(CNArTripp2)(2) and the isoelectronic dinitrogen (N-2) and CO complexes Fe(N-2)(CO)(2)(CNArTripp2)(2) and Fe(CO)(3)(CNArTripp2)(2) demonstrate that the terminal BF ligand possesses particularly strong sigma-donor and pi-acceptor properties. Density functional theory and electron-density topology calculations support this conclusion.