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Issue 5, 2008
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Group 13 metal(I) and (II) guanidinate complexes: effect of ligand backbone on metal oxidation state and coordination sphere

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Abstract

Reactions of lithium salts of the bulky guanidinate and phosphaguanidinate ligands, [ArNC(ER2)NAr] (ER2 = NPri2 (Priso), cis-NC5H8Me2-2,6 (Pipiso) or P(C6H11)2 (PGiso); Ar = C6H3Pri2-2,6), with group 13 metal(I) halides have been carried out. All reactions with TlBr led to monomeric thallium(I) complexes, [Tl{ArNC(ER2)NAr}], in which the ligand chelates the metal in an N,arene-fashion. The reactions with InCl led to mixed results and the isolation of the dimeric indium(II) complexes, [{InCl(Priso)}2] and [{InCl(Pipiso)}2], and the monomeric indium(I) species, [In(Pipiso)] and [In(PGiso)]. The ligands of the latter two complexes exhibit differing coordination modes in the solid state, namely N,N′-chelating and N,arene-chelating, respectively. The reactions with “GaI” were less successful and gave only low yields of the poorly characterised gallium(II) complexes, [{GaI(Priso)}2] and [{GaI(Pipiso)}2]. This study has shown that the related ligand, [ArNC{N(C6H11)2}NAr] (Giso) is superior for the stabilisation of group 13 metal(I) complexes. The oxidative additions of I2 or SiMe3I to one such complex, [Ga(Giso)], yielded the gallium(III) compounds, [GaI2(Giso)] and [GaI(SiMe3)(Giso)].

Graphical abstract: Group 13 metal(i) and (ii) guanidinate complexes: effect of ligand backbone on metal oxidation state and coordination sphere

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Publication details

The article was received on 05 Dec 2007, accepted on 07 Feb 2008 and first published on 14 Mar 2008


Article type: Paper
DOI: 10.1039/B718799H
Citation: New J. Chem., 2008,32, 835-842

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    Group 13 metal(I) and (II) guanidinate complexes: effect of ligand backbone on metal oxidation state and coordination sphere

    G. Jin, C. Jones, P. C. Junk, A. Stasch and W. D. Woodul, New J. Chem., 2008, 32, 835
    DOI: 10.1039/B718799H

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