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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Bonding in transition metal-ether complexes:the spectroscopy and reactivity of the Zr atom-dimethyl ether system
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Bonding in transition metal-ether complexes:the spectroscopy and reactivity of the Zr atom-dimethyl ether system

机译：过渡金属-醚配合物中的键合：Zr原子-二甲醚体系的光谱和反应活性

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The reactivity and bonding of neutral Zr metal atoms with dimethyl ether have been thoroughly characterized using flow tube reactor,PFI-ZEKE,and DFT techniques.Between 275 and 371K,these species form an association complex with the Zr bound to the ether O atom.Using a flow tube reactor,the equilibrium constant for the association reaction has been found to be 6+-2X10~(-14)cm~3 at 361+-10K.From this measure the Zr-dimethyl ether bond energy is estimated to be 80+-2kJ mol~(-1).The ZEKE spectrum of the association complex is reproduced very well by DFT calculations.This calculations indicate that the Zr-dimethyl ether complex is bound by dative bonding involving donation of electron density from the highest occupied dimethyl ether orbital of a_1 symmetry to the Zr 4d orbital of #sigma# symmetry directed along the Zr-dimethyl ether bond axis.Dative bonding interactions are much stronger than donor-acceptor bonding as the vacant dimethl ether antibonding orbital lies too high in energy for back-donation of electron density from Zr to be efficiet.This finding is likely a general characteristic of neutral transition metal-ether complexes.To our knowledge these results constitute the most detailed investigation,to data,to neutral transition metal-ether bonding and reactivity.
机译：使用流管反应器，PFI-ZEKE和DFT技术对中性Zr金属原子与二甲醚的反应性和键合进行了彻底的表征。在275和371K之间，这些物种与Zr结合在醚O原子上形成缔合络合物。使用流动管式反应器，发现在361 + -10K时缔合反应的平衡常数为6 + -2X10〜（-14）cm〜3。据此测得Zr-二甲醚键能为80 + -2kJ mol〜（-1）。通过DFT计算可以很好地再现缔合配合物的ZEKE谱图，表明Zr-二甲醚配合物是通过键合键合的，其中键合键是从最高占据区获得电子密度沿Zr-二甲醚键轴方向与＃sigma＃对称的Zr 4d轨道具有a_1对称性的二甲醚轨道。由于空的二甲基醚反键轨道的能量太高，所以与键-键的相互作用比供体-受体键强得多。从Zr到电子密度的反向捐赠是有效的。这一发现可能是中性过渡金属-醚配合物的一般特征。据我们所知，这些结果构成了对中性过渡金属-醚键合和反应性的最详细的研究。 。

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