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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A Tale of Two Stabilities: How One Boron Atom Affects a Switch in Bonding Motifs in CeO2Bx- (x=2, 3) Complexes
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A Tale of Two Stabilities: How One Boron Atom Affects a Switch in Bonding Motifs in CeO2Bx- (x=2, 3) Complexes

机译：两个稳定性的故事：一个硼原子如何影响CeO2BX-（X = 2,3）复合物中的粘合基序的开关

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摘要

Boronyl (B equivalent to O) ligands have garnered much attention as isoelectronic and isolobal analogues of CO and CN-, yet successful efforts in synthesizing metal boronyl complexes remain scarce. Anion photoelectron (PE) spectroscopy and density functional theory calculations were employed to investigate two small CeO2Bx- (x = 2, 3) complexes generated from laser ablation of a mixed Ce/B pressed powder target. The spectra reveal markedly different bonding upon incorporation of an additional B atom. Most interestingly, CeO2B2- was found to have a Ce(I) center coordinated to two monoanionic boronyl ligands in a bent geometry. This result was unexpected as previous studies suggest electron-rich metals are most suitable for stabilizing such ligands; furthermore, it is one of the first examples of an experimental metal-polyboronyl complex. Introducing another boron atom, however, favors a much different geometry in which Ce(II) coordinates an O2B33- unit through both the O and B atoms, which was evident in the markedly different PE spectra.
机译：硼羰（相当于○B）配体已经赢得了很多关注，CO和CN-的等电子及等瓣类似物，但在合成金属硼羰配合仍然很少成功的努力。阴离子光电子（PE）光谱和密度泛函理论计算进行了用于研​​究两个小CeO2Bx-（X = 2，3）由混合的Ce / B的激光烧蚀产生的复合物压制粉末靶。光谱揭示在一个额外的乙原子的掺入显着不同的键合。最有趣的是，CeO2B2-被发现有弯曲的几何形状与两个单阴离子硼羰配体相铈（I）中心。该结果是出乎意料的，因为之前的研究表明，富含电子的金属是最适合于稳定这样的配体;此外，这是一个实验的金属polyboronyl复合物的第一示例中的一个。引入另一硼原子，但是，有利于大大不同的几何形状，其中铈（II）通过所述O和B两者的原子，这在显着不同的PE光谱是明显的坐标的O2B33-单元。

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