Complexes of four-membered group 13 metal(I) N-heterocyclic carbene analogues with platinum(II) fragments

Moxey, Graeme J., Jones, Cameron, Stasch, Andreas, Junk, Peter C., Deacon, Glen B., Woodul, William D., and Drago, Penny R. (2009) Complexes of four-membered group 13 metal(I) N-heterocyclic carbene analogues with platinum(II) fragments. Dalton Transactions, 2009 (14). pp. 2630-2636.

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A series of fluorinated bis(aryl)platinum(II) complexes, cis-[Pt(Arf)2(1,5-C6H10)] (Arf = p-C6HF4, p-C6(OMe)F4 or C6H2F3−2,4,6) were reacted with the four-membered gallium(I) or indium(I) heterocycles, [:E{[N(Ar)]2CN(C6H11)2}] (E = Ga or In, Ar = C6H3Pri2−2,6) under various stoichiometries. These yielded either the 2:1 complexes, cis-[Pt(Arf)2{Ga{[N(Ar)]2CN(C6H11)2}}2], trans-[Pt(C6H2F3-2,4,6)2{Ga{[N(Ar)]2CN(C6H11)2}}2] and trans-[Pt(Arf)2{In{[N(Ar)]2CN(C6H11)2}}2], or the 3:1 complexes, trans-[Pt(Arf)2{In{[N(Ar)]2CN(C6H11)2}}3] (Arf = p-C6HF4 or p-C6(OMe)F4), all of which were crystallographically characterised. The differing outcomes of these reactions are explained in terms of the lesser nucleophilicity and greater electrophilicity of the indium heterocycle relative to its gallium counterpart. In the solid state, and in solution, the 3:1 indium complexes exhibit strong intramolecular InF interactions which are indicative of their heterocyclic ligands displaying rare examples of "Lewis amphoteric" behaviour. An unusual platinum(0) complex in which the indium(I) heterocycle acts as a µ3-bridging ligand, [{Pt(norbornene)}3{µ3-In{[N(Ar)]2CN(C6H11)2}}2], was also prepared and structurally authenticated.

Item ID: 29691
Item Type: Article (Research - C1)
ISSN: 1477-9234
Keywords: ZN-GA bonds; structural-characterization; gallyl complexes; olefin complexes; crystal-structure; boryl anion; reactivity; gallium(I); aluminum; form
Funders: Australian Research Council (ARC), EPSRC Mass Spectrometry Service at Swansea University
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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