Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 2943-2949 |
| Number of pages | 7 |
| Journal | New Journal of Chemistry |
| Volume | 34 |
| Issue number | 12 |
| Early online date | 19 Sep 2010 |
| DOIs | |
| Publication status | Published - 2010 |
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Iminophosphorane-based [P2N2] rhodium complexes: synthesis, reactivity, and application in catalysed transfer hydrogenation of polar bonds. / Buchard, Antoine; Payet, Elina; Auffrant, Audrey; Goff, Xavier Le; Floch, Pascal Le.
In: New Journal of Chemistry, Vol. 34, No. 12, 2010, p. 2943-2949.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Iminophosphorane-based [P2N2] rhodium complexes: synthesis, reactivity, and application in catalysed transfer hydrogenation of polar bonds
AU - Buchard, Antoine
AU - Payet, Elina
AU - Auffrant, Audrey
AU - Goff, Xavier Le
AU - Floch, Pascal Le
PY - 2010
Y1 - 2010
N2 - [Rh(P2N2)X] complexes (2-X, X = Cl, BF4) featuring a tetradentate iminophosphorane phosphine ligand were synthesised and characterised. X-Ray analysis provides evidence for a square planar geometry without coordination of the chloride anion. These complexes proved to be air-sensitive, and their oxidation to Rh(iii) complexes 3-X was observed in air. The controlled reaction of 2-BF4 with one equivalent of hexachloroethane yielded [Rh(P2N2)Cl2(BF4)] (3-BF4). Direct synthesis of 3-Cl can also be achieved by coordination of the [P2N2] ligand to [RhCl(THT)3] (THT = tetrahydrothiophene). The reactivity of Rh(i) complexes 2 was further investigated, and no reaction was observed with silanes, aryl halides, or pinacolborane, although decomposition was observed under 1 atm of H2 upon prolonged heating. Interestingly, reduction of complex 3-Cl was observed by NMR upon treatment with silanes or sodium isopropoxide. Therefore, complex 3-Cl was used for catalytic transfer hydrogenation of polar bonds. The reduction of aromatic and aliphatic ketones can be carried out using 1% catalyst and 10% sodium isopropoxide, while imines are partially reduced under these conditions.
AB - [Rh(P2N2)X] complexes (2-X, X = Cl, BF4) featuring a tetradentate iminophosphorane phosphine ligand were synthesised and characterised. X-Ray analysis provides evidence for a square planar geometry without coordination of the chloride anion. These complexes proved to be air-sensitive, and their oxidation to Rh(iii) complexes 3-X was observed in air. The controlled reaction of 2-BF4 with one equivalent of hexachloroethane yielded [Rh(P2N2)Cl2(BF4)] (3-BF4). Direct synthesis of 3-Cl can also be achieved by coordination of the [P2N2] ligand to [RhCl(THT)3] (THT = tetrahydrothiophene). The reactivity of Rh(i) complexes 2 was further investigated, and no reaction was observed with silanes, aryl halides, or pinacolborane, although decomposition was observed under 1 atm of H2 upon prolonged heating. Interestingly, reduction of complex 3-Cl was observed by NMR upon treatment with silanes or sodium isopropoxide. Therefore, complex 3-Cl was used for catalytic transfer hydrogenation of polar bonds. The reduction of aromatic and aliphatic ketones can be carried out using 1% catalyst and 10% sodium isopropoxide, while imines are partially reduced under these conditions.
UR - http://www.scopus.com/inward/record.url?scp=78649364658&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1039/C0NJ00299B
U2 - 10.1039/C0NJ00299B
DO - 10.1039/C0NJ00299B
M3 - Article
VL - 34
SP - 2943
EP - 2949
JO - New Journal of Chemistry
JF - New Journal of Chemistry
SN - 1144-0546
IS - 12
ER -