Synthetic, structural and theoretical studies of amidinate and guanidinate stabilised germanium(I) dimers

The neutral germanium(i) dimers, [{Ge(Piso)}(2)] and [{Ge(Giso)}(2)], Piso = [(ArN)(2)CBu(t)](-), Giso = [(ArN)(2)CNPr(i)(2)](-), Ar = C(6)H(3)Pr(i)(2)-2,6, which are stabilised by bulky amidinate and guanidinate ligands respectively, have been prepared by reduction of the corresponding germanium(ii) chlorides, [Ge(Piso)Cl] and [Ge(Giso)Cl]; theoretical studies suggest that the Ge-Ge bonds of [{Ge(Piso)}(2)] and [{Ge(Giso)}(2)] are associated with their HOMOs, whilst their LUMOs have substantial Ge-Ge pi-bonding character.