Homo- and hetero-bridged mixed-valence dinuclear complexes which contain the fragment ‘Rh(C6F5)3’ |
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| Authors: | María P García M Victoria Jimnez Teresa Luengo Luis A Oro |
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| Institution: | Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza, Consejo Superior de Investigaciones Científicas, 50009, Zaragoza, Spain |
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| Abstract: | The reaction of the anionic mononuclear rhodium complex Rh(C6F5)3Cl(Hpz)]t- (Hpz = pyrazole, C3H4N2) with methoxo or acetylacetonate complexes of Rh or Ir led to the heterodinuclear anionic compounds (C6F5)3Rh(μ-Cl)(μ-pz)M(L2)] M = Rh, L2 = cyclo-octa-1,5-diene, COD (1), tetrafluorobenzobarrelene, TFB (2) or (CO)2 (4); M = Ir, L2 = COD (3)]. The complex Rh(C6F5)3(Hbim)]? (5) has been prepared by treating Rh(C6F5)3(acac)]? with H2bim (acac = acetylacetonate; H2bim = 2,2′-biimidazole). Complex 5 also reacts with Rh or Ir methoxo, or with Pd acetylacetonate, complexes affording the heterodinuclear complexes (C6F5)3Rh(μ-bim)M(L2)]? M = Rh, L2 = COD (6) or TFB (7); M = Ir, L2 = COD (8); M = Pd, L2 = η3-C3H5 (9)]. With Rh(acac)(CO)2], complex 5 yields the tetranuclear complex {(C6F5)3Rh(μ-bim)Rh(CO)2}2]2?. Homodinuclear RhIII derivatives {Rh(C6F5)3}2(μ-L)2]·- L2 = OH, pz (11); OH, StBu (12); OH, SPh (13); bim (14)] have been obtained by substitution of one or both hydroxo groups of the dianion {Rh(C6F5)3(μ-OH)}2]2? by the corresponding ligands. The reaction of Rh(C6F5)3(Et2O)x] with PdX2(COD)] produces neutral heterodinuclear compounds (C6F5)3Rh(μ-X)2Pd(COD)] X = Cl (15); Br (16)]. The anionic complexes 1–14 have been isolated as the benzyltriphenylphosphonium (PBzPh3+) salts. |
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| Keywords: | Rhodium Palladium Iridium Heteronuclear bridged species Homonuclear bridged species Syntheses |
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