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The synthesis of the tripodal phosphine CH3C{CH2P(m-CF3C6H4)2}3 and its rhodium coordination chemistry |
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| Authors: | Sülü Mustafa Luigi M Venanzi Tobias Gerfin Volker Gramlich |
| Institution: | aLaboratorium für Anorganische Chemie, ETH Zentrum, Universitätstrasse 6, CH-8092 Zurich, Switzerland bFaculty of Art and Sciences, Inönü University, TR-44100 Malatya, Turkey cInstitut für Kristallographie und Petrographie, ETH Zentrum, Sonneggstrasse 5, CH-8092 Zurich, Switzerland |
| Abstract: | The new tripodal phosphine CH3C{CH2P(m-CF3C6H4)2}3, CF3PPP, was prepared by reacting CH3C(CH2Br)3 with Li+P(m-CF3C6H4)2−, the latter being best obtained by adding Li+NiPr2− to PH(m-CF3C6H4)2. The rhodium complexes RhCl(CO)(CF3PPP)], Rh(LL)(CF3PPP)](CF3SO3) (LL = 2 CO or NBD), RhX3(CF3PPP)], RhX(MeCN)3(CF3PPP)](CF3SO3)2 (X = H and Cl), RhCl2(MeCN)(CF3PPP)](CF3SO3) and Rh(MeCN)3(CF3PPP)](CF3SO3)3 were prepared and characterized. The X-ray crystal structure of Rh(NBD)(CF3PPP)](CF3SO3) is reported. The lower oxygen sensitivity of the CF3PPP rhodium(I) complexes, relative to the corresponding species with the parent ligand CH3C(CH2PPh2)3, is attributed to the higher effective nuclear charge on the metal centers caused by the presence of the six CF3 substituents on the terdentate phosphine. A similar effect may be responsible for the easier hydrolysis of the CF3PPP-containing, cationic rhodium(III) complexes relative to the corresponding compounds of the parent ligand. |
| Keywords: | Tripodal phosphine complexes CF3-substituted phosphine complexes Rhodium complexes Crystal structures |
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