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Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands 下载免费PDF全文
Dr. Mario Carrasco Irene Mendoza Dr. Eleuterio Álvarez Dr. Abdessamad Grirrane Dr. Celia Maya Dr. Riccardo Peloso Dr. Amor Rodríguez Andrés Falceto Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):410-421
To clarify the nature of the Mo?Carene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo2(Ar′)(I)(O2CR)2(OEt2)] have been prepared and characterized (Ar′=ArXyl2, R=Me; Ar′=ArMes2, R=Me; Ar′=ArXyl2, R=CF3) (Mes=mesityl; Xyl=2,6‐Me2C6H3, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe3, P(OMe)3 and PiPr3 were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN2C2Me4 (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo2(Ar′)(I)(O2CR)2( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo2(ArXyl2)(O2CMe)2(CN2C2Me4)2]I. The Mo?Carene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and Carene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules. 相似文献
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Dr. Joice Thomas Dr. Liliana Dobrzańska Prof. Luc Van Meervelt Prof. Mario Alfredo Quevedo Prof. Krzysztof Woźniak Marcin Stachowicz Prof. Mario Smet Prof. Wouter Maes Prof. Wim Dehaen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):979-987
A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles. 相似文献