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Issue 41, 2011
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Synthesis and structures of homo- and heterobimetallic rhodium(I) and/or iridium(I) complexes of binucleating bis(1-pyrazolyl)methane ligands

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Abstract

The synthesis of a series of Rh(I) and Ir(I) homobimetallic complexes using three different linking scaffolds is described. The cyclooctadiene (COD) complexes [M2(COD)2(Lscaffold)][BArF4]2 (2–7) where M = Rh(I) or Ir(I), and Lscaffold = bis(1-pyrazolyl)methane ligands, p-C6H4[CH(pz)2]2 (1a), m-C6H4[CH(pz)2]2 (1b) and the anthracene-bridged 1,8-C14H8[CH(pz)2]2 (1c) were synthesized. The COD co-ligands of 2–7 were replaced with the carbonyl co-ligands to form the analogous homobimetallic complexes, [M2(CO)4(Lscaffold)][BArF4]2 (8–13). The solid-state structures of the dicationic homobimetallic complexes 2, 3, 5, 6, 9, and 10, as well as cationic monometallic complexes 15 and 22 of ligands 1b and 1c respectively, were characterized using X-ray crystallography. The solid-state XRD structures of the resulting dirhodium and diiridium complexes with the para- and meta-phenylene and anthracene scaffolds show that there are distinct differences between structures of complexes 2–10 due to the variation in the scaffold structures, in particular the relative positions of the two metal centres. Heterobimetallic RhIr complexes of the m-C6H4[CH(pz)2]2 ligand were also synthesized using a stepwise approach, and the observed exchange of the metal centres in the heterobimetallic complexes was found to be dependent on the nature of the coligand.

Graphical abstract: Synthesis and structures of homo- and heterobimetallic rhodium(i) and/or iridium(i) complexes of binucleating bis(1-pyrazolyl)methane ligands

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Publication details

The article was received on 24 Mar 2011, accepted on 09 Aug 2011 and first published on 16 Sep 2011


Article type: Paper
DOI: 10.1039/C1DT10499C
Dalton Trans., 2011,40, 11031-11042

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    Synthesis and structures of homo- and heterobimetallic rhodium(I) and/or iridium(I) complexes of binucleating bis(1-pyrazolyl)methane ligands

    J. H. H. Ho, J. Wagler, A. C. Willis and B. A. Messerle, Dalton Trans., 2011, 40, 11031
    DOI: 10.1039/C1DT10499C

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