Step-by-step uncoordination of the pyrazolyl rings of hydrotris(pyrazolyl)borate ligands in complexes of RhI and RhIII
| Autor: | Paneque, Margarita, Sirol, Sabine, Trujillo, Marianela, Carmona, Ernesto, Gutiérrez-Puebla, Enrique, Monge, M. Ángeles, Ruiz, Caridad, Malbosc, F., Serra-Le Berre. C. Etienne, M., Daran J.C. |
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| Rok vydání: | 2001 |
| Předmět: | |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | Compounds of rhodium(I) and rhodium(III) that contain ancillary hydrotris(pyrazolyl)borate ligands (Tp′) react with monodentate and bidentate tertiary phosphanes in a step-wise manner, with incorporation of P-donor atoms and concomitant replacement of the Tp′ pyrazolyl rings. Accordingly, [Rh(κ3-TpMe2)(C2H4)(PMe 3)] (1b), converts initially into [Rh(κ2-TpMe2)-(PMe3)2] (3), and then into [Rh(κ1-TpMe2-(PMe3)3] (2) upon interaction with PMe3 at room temperature, in a process which can be readily reversed under appropriate experimental conditions. Full disengagement of the Tp′ ligand is feasible to give Tp′ salts of rhodium(I) complex cations, for example, [Rh(CO)(dppp)2]-[TpMe2,4-Cl] (5; dppp = Ph2P(CH2)3PPh2), or [Rh(dppp)2][TpMe2,4-Cl] (6). Bis(hydride) derivatives of rhodium(III) exhibit similar substitution chemistry, for instance, the neutral complex [Rh(Tp)-(H)2(PMe3)] reacts at 20°C with an excess of PMe3 to give [Rh(H)2-(PMe3)4][Tp] (9b). Single-crystal X-ray studies of 9b, conducted at 143 K, demonstrate the absence of bonding interactions between the [Rh(H)2(PMe3)4]+ and Tp ions, the closest Rh⋯N contact being at 4.627 Å. © Wiley-VCH Verlag GmbH, 2001. |
| Databáze: | OpenAIRE |
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