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Título: | An entry to stable mixed phosphine–osmium–NHC polyhydrides |
Autor: | Buil, María L. CSIC ORCID; Cardo, Juan F. CSIC; Esteruelas, Miguel A. CSIC ORCID; Fernández, Israel; Oñate, Enrique CSIC ORCID | Fecha de publicación: | 2016 | Editor: | American Chemical Society | Citación: | Inorganic Chemistry 55(10): 5062-5070 (2016) | Resumen: | An entry to mixed phosphine–osmium–NHC polyhydride complexes is described, starting from the five-coordinate hydrido–alkylidyne compounds [OsHCl(≡CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = PiPr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os–C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η2-H-BCH2Ph)(IPr)(PR3) (PR3 = PiPr3 (3), PPh3 (4)) or OsH2(η2:η2:H2BCH2Ph)(IPr)(PiPr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride–trihydride OsH3Cl(IPr)(PiPr3)2 (6), which reacts with NaBH4 to give OsH3(κ2-H2BH2)(IPr)(PiPr3) (7). This trihydride–tetrahydrideborate derivative and its PPh3 counterpart OsH3(κ2-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at −60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-borane derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d2-hexahydride derivatives OsH6(IPr)(PR3) (PR3 = PiPr3 (9), PPh3 (10)), which reduce the C≡N triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ2-N,C-(NH═CH-C6H4)}(IPr)(PR3)2 (PR3 = PiPr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine. | Versión del editor: | http://dx.doi.org/10.1021/acs.inorgchem.6b00658 | URI: | http://hdl.handle.net/10261/133241 | DOI: | 10.1021/acs.inorgchem.6b00658 | ISSN: | 0020-1669 | E-ISSN: | 1520-510X |
Aparece en las colecciones: | (ISQCH) Artículos |
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NHC Polyhydrides.pdf | 677,9 kB | Adobe PDF | Visualizar/Abrir |
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