N2-Cu-F:: A complex of dinitrogen and cuprous fluoride characterized by rotational spectroscopy
N2-Cu-F:: A complex of dinitrogen and cuprous fluoride characterized by rotational spectroscopy
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DOI：
10.1002/anie.200601988
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Legon, Anthony C.
中科院分区：
文献类型：
--
作者：
Francis, Simon G.;Matthews, Steven L.;Legon, Anthony C.
从大气氮固定的角度来看，人们对过渡金属与氮素反应产生的化合物的鉴定和表征有长期的普遍兴趣。此外，由于氮气和一氧化碳的等电子、等规性质，研究氮气与过渡金属化合物的相互作用具有内在的意义。关于过渡金属羰基化合物有大量的文献[1]，从中可以得出这样的结论：在这类化合物中，CO与过渡金属中心之间普遍存在着很强的成键作用。最近，一系列简单的线性过渡金属羰基化合物OC、M和X(M=铜，[2]Ag，[3]或Au[4]；X=F，Cl，或Br.)在气相中通过旋转光谱对它们的几何和电子结构进行了详细的研究。关于金属中心电荷再分布的信息包含在M=Cu或Au的核四极耦合常数中。在这些过渡物种中，CO和M之间的相互作用也很强。另一方面，至少在形式上可以设想的氢键物种OC··H和X是通过用H取代M而从OC和M和X生成的。[5-7]这类配合物是弱结合的(这里用···)，分子间结合能仅为几个kJmo1。氮配合物N_2···H和X具有与OC···H和X相似的线性几何构型，但氢键略弱。[8-10]可以通过假设HX的亲电区寻找CO或N2的最亲核区(即非键轴)来理解OC··H·HOX和N2··H·HOX的同构性质。
From the viewpoint of the fixation of atmospheric nitrogen, there is a long-term general interest in the identification and characterization of compounds that result from the reaction of transition metals with dinitrogen. In addition, the investigation of the interaction of N2 with transition-metal compounds has intrinsic significance because of the isoelectronic, isolobal nature of dinitrogen and carbon monoxide. There is a voluminous amount of literature [1] on transition-metal carbonyl compounds, from which it is concluded that the nature of the generally strong bonding interaction of CO with the transition-metal center in such compounds is well-understood.Recently, a series of simple linear transition-metal carbonyl complexes of the type OCĀMĀX (M= Cu,[2] Ag,[3] or Au [4]; X= F, Cl, or Br) were thoroughly investigated in the gas phase by means of their rotational spectra to give details of their geometry and electronic structure. Information about the electric-charge redistribution at the metal center is contained in the nuclear quadrupole coupling constants for M= Cu or Au. The interaction between CO and M was also found to be strong in these transient species. On the other hand, the hydrogen-bonded species OC··· HĀX, which may be envisaged, formally at least, as generated from OCĀMĀX by replacement of M by H, have been investigated extensively by rotational spectroscopy.[5–7] Such complexes are weakly bound (here depicted with···) with intermolecular binding energies of only a few kJmolĀ1. The dinitrogen complexes N2··· HĀX have linear geometries similar to those of OC··· HĀX, but with slightly weaker hydrogen bonds.[8–10] The isostructural nature of OC··· HĀX and N2··· HĀX can be understood by assuming that the electrophilic region of HX seeks the most nucleophilic region of CO or N2 (namely, the axis of a nonbonding