The reaction of the 2,6-bis­(imino)­phenylchlorogermylene [LGeCl] (1, L = C6H3-2,6-(HC​NtBu)2) with silver­(I) trifluoromethanesulfonate (AgOTf) in a molar ratio of 2:3 in toluene afforded a mixture of the bis­(germylene)­silver­(I) complex [{L­(TfO)­Ge}2­Ag­(OTf)] (2) and AgCl. Compound 2 was then reacted with 2 equiv of 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene (IMe, :C­{N­(Me)­C­(Me)}2) in toluene to afford 3, which comprises the bis­(germyliumylidene)­silver­(I) complex dication [{L­(IMe)­Ge}2­Ag­(OTf)]2+. Compounds 2 and 3 were characterized by NMR spectroscopy and X-ray crystallography. [{L­(IMe)­Ge}2­Ag­(OTf)]2+ in compound 3 was further elucidated by DFT studies.

The reactivity of the 2-imino-5,6-methylenedioxylphenylgermanium(I) dimer toward group 9 metal(I) chloride and dimanganese decacarbonyl is described. [LGe:] (1, L = 2-imino-5,6-methylenedioxylphenyl) underwent a disproportionation reaction with 1.5 equiv of group 9 metal(I) chloride [MCl(cod)] (M = Rh, Ir) in toluene to afford a mixture of the group 9 metallogermylene-chlorometal(I) complexes [LGeμ-{M(cod)}Cl] (M = Rh (2), Ir (4)) and chlorogermylene-chlorometal(I) complexes [L(Cl)GeM(cod)Cl] (M = Rh (3), Ir (5)), respectively. The disproportionation property of 1 is further evidenced by its reaction with 0.5 equiv of Mn(CO) in refluxing toluene to form a mixture of the manganogermylene dimer [(LGe)μ-{Mn(CO)}] (7) and free ligand [LH] (8). Compounds 2-5, 7, and 8 were elucidated by NMR spectroscopy, X-ray crystallography, and DFT calculations, respectively.

The trapping of a transient base-stabilized germylenylsilylene by elemental tellurium and arylazide is described. The reaction of the potassium 2-imino-5,6-methylenedioxylphenylgermylidenide [L iminophenyl GeK] (L iminophenyl = 2-imino-5,6-methylenedioxylphenyl) with the amidinato chlorosilylene [L amidinate SiCl] {L amidinate = PhC(NtBu) 2 } in THF at-78°C afforded the transient base-stabilized germylenylsilylene [L amidinate SiGeL iminophenyl ] (3). It was unstable in solution, but can be trapped by reacting with elemental tellurium and 2,6-diiso-[a] Dr.

The reaction of amidinato phosphinoamidosilylene 1 with GeCl2·dioxane in toluene afforded a dimeric phosphine-stabilized phosphidogermanium(i)–amidogermanium(ii) derivative 3 and a mixture of by-products. Compound 3 is the first example comprising a novel phosphidogermanium(i) dimer moiety [Ph2P-Ge:]2, being considered as a base-stabilized diphosphidoditetrelyne derivative.

Correction for ‘Synthesis of a dimeric phosphine-stabilized phosphidogermanium(i)–amidogermanium(ii) derivative’ by Muhammad Luthfi Bin Ismail et al., Chem. Commun., 2019, DOI: 10.1039/c8cc09454c.