Ruthenophanes: Evaluating Cation鈭捪€ Interactions in [Ru(畏6-C16H12R4)(NH3)3]2+/3+ Complexes. A Computational Insight

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• 作者：Giovanni F. Caramori ; Leone C. Garcia ; Diego M. Andrada ; Gernot Frenking
• 刊名：Organometallics
• 出版年：2014
• 出版时间：May 12, 2014
• 年：2014
• 卷：33
• 期：9
• 页码：2301-2312
• 全文大小：625K
• 年卷期：v.33,no.9(May 12, 2014)
• ISSN：1520-6041

文摘

The nature of cation鈭捪€ interactions in a set of [Ru(畏⁶-C₁₆H₁₂R₄)(NH₃)₃]²⁺³⁺ (R = F, CN, CH₃, and others), complexes was investigated with Su鈥揕i energy decomposition analysis and the natural orbitals for chemical valence and the extended transition state method EDA-NOCV. The long-distance effects of electron-donating and electron-withdrawing substituents as well as protonation of the ipso carbon on the nature of cation鈭捪€ interactions were investigated. Both energy decomposition analyses, Su鈥揕i EDA and EDA-NOCV, are in total agreement, showing that the presence of electron-donating substituents such as CH₃, NH₂, and H₃CO tends to stabilize the ruthenium鈥揳rene interaction while electron-withdrawing substituents such as F, CN, and NO₂ tend to weaken such interactions. The electrostatic component of the ruthenium鈥揳rene interaction is the most affected by the substitution, despite the fact that the covalent character is much more significant than the electrostatic character. EDA-NOCV reveals that the most important orbital stabilization comes from donation and back-donation between the interacting fragments, while the 蟽 density deformations present a moderate contribution to total orbital stabilization energy in ruthenium鈥揳rene interactions of complexes 1鈥?b>8.