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

Jin, Guoxia, Jones, Cameron, Junk, Peter C., Stasch, Andreas, and Woodul, William D. (2008) Group 13 metal(I) and (II) guanidinate complexes: effect of ligand backbone on metal oxidation state and coordination sphere. New Journal of Chemistry, 32 (5). pp. 835-842.

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View at Publisher Website: http://dx.doi.org/10.1039/b718799h
 
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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)].

Item ID: 29628
Item Type: Article (Research - C1)
ISSN: 1369-9261
Keywords: heterocyclic carbene analogs; thallium(i) complexes; chemistry; aluminum; gallium; reactivity; fragments; compound; elements; anion
Funders: Australian Research Council (ARC), Royal Society
Date Deposited: 02 Oct 2013 10:34
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030204 Main Group Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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