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)

  1. Elduque, A. 1
  2. Aguilera, Francisco . 1
  3. Lahoz, F.J. 1
  4. Löpez, J.A. 1
  5. Oro, L.A. 1
  6. Pinillos, M.T. 2
  1. 1 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  2. 2 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Journal:
Inorganica Chimica Acta

ISSN: 0020-1693

Year of publication: 1998

Volume: 274

Issue: 1

Pages: 15-23

Type: Article

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DOI: 10.1016/S0020-1693(97)05963-X SCOPUS: 2-s2.0-0003163774 WoS: WOS:000073916500003 GOOGLE SCHOLAR

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Abstract

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.