Density functional theory study of substituent effects on gas-phase heterolytic Fe-N bond energies of m-G-C6H4NHFe(CO)2(η5-C5H5) and m-G-C6H4N(COMe)Fe(CO)2(η5-C5H5)

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2024-09-12 DOI:10.1016/j.ica.2024.122370

Qing Zeng , Zucheng Li , Yi-Bo Wang

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Abstract

The nature and strength of metal–ligand bonds in organotransition-metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe-N bond energies of meta-substituted anilinyldicarbonyl(η⁵-cyclopentadienyl)iron [m-G-C₆H₄NH(η⁵-C₅H₅)Fe(CO)₂, abbreviated as m-G-C₆H₄NHFp (1), where G=NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO and NMe₂] and meta-substituted α-acetylanilinyldicarbonyl(η⁵-cyclopentadienyl)iron [m-G-C₆H₄N(COMe)(η⁵-C₅H₅)Fe(CO)₂, abbreviated as m-G-C₆H₄N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe-N)′s. ΔΔH_het(Fe-N)′s (1 and 2) conform to the captodative principle. There are excellent linear free energy relations among ΔΔH_het(Fe-N)′s and the experimental and computational substituent effects on acidities of m-G-C₆H₄NH₂, the differences of acidic dissociation constants (ΔpK_as) of NH bonds for m-G-C₆H₄NH₂ for series 1 or the substituent σ_m constants. The former correlations imply that the govering factors for these bond scissions are similar; the latter ones suggest that polar effects of meta-substituents show the dominant role to the magnitudes of ΔH_het(Fe-N)′s. And these correlations are in accordance with Hammett linear free energy relationships. The Fe-N bonds in series 1 are stronger than those in series 2. Therefore m-G-C₆H₄N(COMe)^- are more stable than m-G-C₆H₄NH^-. The absolute magnitudes of AEs, AE_α-COMes and AE_α-COMe, _para_-Gs are far larger than MEs, ME_α-COMes and ME_α-COMe, _para_-Gs. The influences of MEs, ME_α-COMes and ME_α-COMe, _para_-Gs are subtle. A better understanding of organometallic bond energies can suggest whether proposed new catalytic systems may work well.

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取代基对 m-G-C6H4NHFe(CO)2(η5-C5H5) 和 m-G-C6H4N(COMe)Fe(CO)2(η5-C5H5) 的气相异解 Fe-N 键能影响的密度泛函理论研究

有机过渡金属配合物中金属配体键的性质和强度对于理解有机金属反应和催化作用至关重要。不同理论水平的量子化学计算被用来研究元取代苯胺基二羰基（η5-环戊二烯基）铁[m-G-C6H4NH(η5-C5H5)Fe(CO)2，缩写为 m-G-C6H4NHFp (1)]的异溶解 Fe-N 键能、其中 G=NO2、CN、COMe、CO2Me、CF3、Br、Cl、F、H、Me、MeO 和 NMe2]以及元取代的 α-乙酰苯胺基二羰基（η5-环戊二烯基）铁[m-G-C6H4N(COMe)(η5-C5H5)Fe(CO)2，缩写为 m-G-C6H4N(COMe)Fp (2)]配合物。结果表明，在研究ΔHhet(Fe-N)′s 时，BP86 和 TPSSTPSS 具有最佳的性价比和更精确的预测。ΔΔHhet(Fe-N)′s与实验和计算中取代基对 m-G-C6H4NH2 酸性的影响、1 系列 m-G-C6H4NH2 NH 键酸性解离常数 (ΔpKas)的差异或取代基 σm 常数之间存在极好的线性自由能关系。前者的相关性意味着这些键裂解的影响因素是相似的；后者则表明元取代基的极性效应对 ΔHhet(Fe-N)′s的大小起着主导作用。这些相关性与 Hammett 线性自由能关系相一致。系列 1 中的 Fe-N 键比系列 2 中的强。因此，m-G-C6H4N(COMe)- 比 m-G-C6H4NH- 更稳定。AEs, AEα-COMes 和 AEα-COMe, para-Gs 的绝对值远远大于 MEs, MEα-COMes 和 MEα-COMe, para-Gs。MEs、MEα-COMes 和 MEα-COMe, para-Gs 的影响是微妙的。更好地了解有机金属键的能量可以说明所提出的新催化体系是否能很好地发挥作用。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.