Oxidative addition of methyl iodide and iodine to new binuclear rhodium(I) and iridium(I) compounds containing diaminoanthraquinonate-bridging ligands. Crystal structure of [Rh2(μ-1,4-DA)(CO)2(PPh3)2] (1,4-H2DA = 1,4-diaminoanthraquinone)
- Elduque, A. 1
- Aguilera, Francisco . 1
- Lahoz, F.J. 1
- Löpez, J.A. 1
- Oro, L.A. 1
- Pinillos, M.T. 2
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1
Instituto de Nanociencia y Materiales de Aragón
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2
Universidad de La Rioja
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ISSN: 0020-1693
Año de publicación: 1998
Volumen: 274
Número: 1
Páginas: 15-23
Tipo: Artículo
beta Ver similares en nube de resultadosOtras publicaciones en: Inorganica Chimica Acta
Resumen
The binuclear rhodium and iridium complexes containing the 1,4-diaminoanthraquinonate ligand (1,4-DA) [M2(μ-1,4-DA)L2] (L = COD, M = Rh (1), Ir (2); L = (CO)2, M = Rh (3), Ir (4); L = (CO) (PPh3), M = Rh (5), Ir (6)) have been prepared and oxidative addition of the electrophiles MeI and I2 has been investigated. The molecular structure of an isomer of compound 5 has been determined by X-ray diffraction methods. Complex 5a crystallised in the triclinic space group P-1, with a = 9.711 (5), b = 13.701(7), c = 17.990(9) Å, α=68.53(2), β=76.98(3), γ=79.72(3)°, and Z=2. The molecule is binuclear with the metals bridged by an approximately planar tetradentate dianionic 1,4-DA ligand. Both rhodium centres exhibit slightly distorted square-planar coordinations with both phosphine groups trans disposed to the aminic nitrogen atoms. Addition of MeI to the rhodium complex 5 leads to the diacyl-dirhodium(III) derivative [Rh2(μ-1,4-DA)(COMe)2I2(PPh 3)2] (7). However, addition of MeI to the isoelectronic iridium compound 6 yields the dimethyl-diiridium(III) compound [Ir2(μ-1,4-DA)I2(Me)2(CO) 2(PPh3)2] (8). Reaction of iodine with compounds 5 or 6, in a molar ratio M/I2=1/1, yields the symmetrical complexes [M2(μ,-1,4-DA)I4(CO)2(PPh3) 2] (M=Rh (9), Ir(10)). © 1998 Elsevier Science S.A. All rights reserved.