On the reactivity of Al-group 11 (Cu, Ag, Au) bonds

Reactions of the seven-membered heterocyclic potassium diamidoalumanyl, [K{Al(SiN^Dipp)}]₂ (SiN^Dipp = {CH₂SiMe₂NDipp}₂; Dipp = 2,6-di-isopropylphenyl), with a variety of Cu(I), Ag(I) and Au(I) chloride N-heterocyclic carbene (NHC) adducts are described. The resultant group 11-Al bonded derivatives have been characterised in solution by NMR spectroscopy and, in the case of [{SiN^Dipp}Al-Au(NHC^iPr)] (NHC^iPr = N,N'-di-isopropyl-4,5-dimethyl-2-ylidene), by single crystal X-ray diffraction. Although similar reactions of LAgCl and LAuCl, where L is a more basic cyclic alkyl amino carbene (CAAC), generally resulted in reduction of the group 11 cations to the base metals, X-ray analysis of [(^CyCAAC)AgAl(SiN^Dipp)] (^CyCAAC = 2-[2,6-bis(1-methylethyl)phenyl]-3,3-dimethyl-2-azaspiro[4.5]dec-1-ylidene) provides the first solid-state authentication of an Ag-Al σ bond. The reactivity of the NHC-supported Cu, Ag and Au alumanyl derivatives was assayed with the isoelectronic unsaturated small molecules, N,N'-di-isopropylcarbodiimide and CO₂. While these reactions generally provided products consistent with nucleophilic attack of the group 11 atom at the electrophilic heteroallene carbon centre, treatment of the NHC-supported copper and silver alumanyls with N,N'-di-isopropylcarbodiimide yielded less symmetric Cu-C and Ag-C-bonded isomers. In contrast to the previously described copper and silver alumanyl derivatives, [(NON)Al(O₂C)M(Pt-Bu₃)] (M = Cu or Ag; NON = 4,5-bis(2,6-di-isopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), which were prone to facile CO extrusion and formation of carbonate derivatives, the NHC-supported dioxocarbene species, [(NHC^iPr)M(CO₂)Al(SiN^Dipp)] (M = Cu, Ag, Au), are all stable at room and moderately elevated temperatures. The stabilising role of the NHC co-ligand was, thus, assessed by preparation of the t-Bu₃P adducted copper-alumanyl, [(t-Bu₃P)CuAl(SiN^Dipp)]. Treatment of this latter compound, which was also structurally characterised by X-ray analysis, with both N,N'-di-isopropylcarbodiimide and CO₂ again provided smooth heteroallene insertion and formation of the relevant Cu-C-bonded products. Although both compounds were quite stable at room temperature, heating of [(t-Bu₃P)Cu(CO₂)Al(SiN^Dipp)] at 60 °C induced elimination of CO and formation of the analogous carbonate, [(t-Bu₃P)Cu(OCO₂)Al(SiN^Dipp)], which was identified by ¹³C and ³¹P NMR spectroscopy. Reflective of the more reliable nucleophilic behaviour of the gold centres in these group 11 alumanyls, computational (QTAIM and NBO) analysis highlighted a lower level of covalency of the Al-Au linkage in comparison to the analogous Al-Cu and Al-Ag interactions. Although substitution of the co-ligand significantly perturbs the charge distribution across the Cu-Al bond of [LCuAl(SiN^Dipp)] (L = NHC^iPr or t-Bu₃P), only a negligible difference is observed between the phosphine-coordinated copper systems derived from either the [SiN^Dipp]- or (NON)-based alumanyl ligands. Computational mapping of the reaction profiles arising from treatment of the various group 11 alumanyls with N,N'-di-isopropylcarbodiimide indicates that the observed formation of the Cu-N and Ag-N bound isomers do not provide the thermodynamic reaction outcome. In contrast, examination of the CO₂-derived reactions, and their potential toward CO extrusion and subsequent carbonate formation, implies that the identity of the co-ligand exerts a greater influence on this aspect of reactivity than the architecture of the diamidoalumanyl anion.