Evaluating stereoelectronic properties of bulky dialkylterphenyl phosphine ligands
| Autor: | María M. Alcaide, Joaquín López-Serrano, Ernesto Carmona, Juan J. Moreno, Eleuterio Álvarez, Jesús Campos, M. Carmen Nicasio, Mario Marín |
|---|---|
| Přispěvatelé: | Universidad de Sevilla. Departamento de Química Inorgánica, Ministerio de Ciencia, Innovación y Universidades (MICINN). España |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Steric effects
Terphenyl Substituent chemistry.chemical_element Bulky phosphine 010402 general chemistry 01 natural sciences Biochemistry Rhodium Inorganic Chemistry chemistry.chemical_compound Materials Chemistry Ligand cone angle Iridium Physical and Theoretical Chemistry 010405 organic chemistry Ligand Organic Chemistry 0104 chemical sciences Tolman Selenides chemistry Ligand parameterization Physical chemistry Buried volume Phosphine |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | The stereoelectronic properties of a series of sterically hindered phosphines containing a terphenyl substituent, PR2Ar’ (R = alkyl; Ar’ = C6H3-2,6-Ar2), have been evaluated by various methods. Their σ-donating capacity has been assessed on the basis of the carbon monoxide stretching frequencies in benchmark iridium [IrCl(CO)2(PR2Ar’)] and rhodium [Rh(acac)(CO)2(PR2Ar’)] (acac = acetylacetonate) complexes, as well as by measuring 31P–77Se scalar coupling constants (1JSeP) for the corresponding phosphine selenides (Se=PR2Ar’). In turn, the steric profile of terphenyl phosphines has been gauged by calculating Tolman Cone Angle (TCA), ligand shielding (G) and percent buried volume (%VBur) parameters. These calculations have been carried out from both X-ray diffraction and DFT-optimized structures. We have also examined several of the widely used biaryl phosphines for comparative purposes. Ministerio de Ciencia, Innovación y Universidades CTQ2013-42501-P, CTQ2016-75193P, CTQ2014-52769-C3-3-R, CTQ2017-82893-C2-2-R |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|