Oxidative Addition of Secondary Phosphine Oxides through Rh(I) Center: Hydrido-Phosphinito-Rh(III) Complexes and their Catalytic Activity in Hydrophosphinylation of Alkynes
[EN]The reaction of [Rh(mu-Cl)(cod)](2) with diimines, differing in their steric and electronic properties, and with diphenylphosphine oxide leads to the oxidative addition products, hydrido-phosphinito-Rh(III) complexes {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} (1), stabilized by the formation of a hydrogen bon...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universidad del País Vasco |
| Repositorio: | Addi. Archivo Digital para la Docencia y la Investigación |
| OAI Identifier: | oai:addi.ehu.eus:10810/54838 |
| Acceso en línea: | http://hdl.handle.net/10810/54838 |
| Access Level: | acceso abierto |
| Palabra clave: | hydrophosphinylation organometallic chemistry oxidative addition rhodium secondary phosphine oxides |
| Sumario: | [EN]The reaction of [Rh(mu-Cl)(cod)](2) with diimines, differing in their steric and electronic properties, and with diphenylphosphine oxide leads to the oxidative addition products, hydrido-phosphinito-Rh(III) complexes {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} (1), stabilized by the formation of a hydrogen bonded phosphinous acid-phosphinito quasi-chelate [(PO...HOP)-kappa P-2]. Exchange of hydride by chloride to afford {Rh(PPh2OH)(PPh2O)(NN)Cl-2} (2) occurs in hydrido complexes containing low steric hindrance diimines and is inhibited for complexes containing encumbered diimines. Complexes 1 react with BF3.OEt2 with exchange of the acidic proton by BF2, and transformation of the quasi-chelating PO...HOP into a chelating PO-BF2-OP ligand in {Rh{(PPh2O)(2)BF2}(NN)(H)Cl} (3). The reaction of [Rh(mu-Cl)(nbd)](2) or [Rh(acac)(nbd)] with diphenylphosphine oxide leads to coordinatively unsaturated nortricyclyl-phosphinito-Rh(III) complexes, {Rh(PPh2OH)(PPh2O)(ntyl)(mu-Cl)}(2) (4) or {Rh(PPh2OH)(PPh2O)(ntyl)(acac)} (6), respectively. Their reaction with BF3.OEt2 results in the corresponding {Rh{(PPh2O)(2)BF2}(ntyl)(mu-Cl)}(2) (5) or {Rh{(PPh2O)(2)BF2}(ntyl)(acac)} (7). Some of these new complexes have shown catalytic activity in hydrophosphinylation of alkynes, with {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} containing encumbered NN being efficient and regioselective catalysts in the hydrophosphinylation of phenylacetylene with diphenylphosphine oxide to produce (E)-diphenyl(styryl)phosphine oxide. |
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