Experimental and Computational Studies of the Molybdenum-Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands
To clarify the nature of the Mo[BOND]Carene interaction in terphenyl complexes with quadruple Mo[BOND]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...
| Autores: | , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2015 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/64445 |
| Acceso en línea: | http://hdl.handle.net/11441/64445 https://doi.org/10.1002/chem.201404057 |
| Access Level: | acceso abierto |
| Palabra clave: | Density fuctional calculations Lewis bases Molybdenum Quadrupel bonds Therphenyl ligands |
| Sumario: | To clarify the nature of the Mo[BOND]Carene interaction in terphenyl complexes with quadruple Mo[BOND]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[BOND]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[BOND]Mo, Mo[BOND]X, and Mo[BOND]L bonds present in these molecules. |
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