A Bis(germyliumylidene)silver(I) Complex Dication

Abstract

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.

Preparation and Molecular Structure of a Cationic Bisplumbylene

“…Silver salts and electron deficient group 13 compounds are established reagents for the abstraction of halides . In this vein organolead cations have been obtained via demethylation and dechlorination of respective heteroleptic Pb(II)‐compounds with electron deficient boranes.…”

“…The 27 Al NMR spectra show a sharp resonance (ν 1/2 = 36 Hz) at +104.0 ppm which is the region typical for highly symmetric tetrahedral aluminum species. [10d], By contrast, no well‐resolved 207 Pb NMR spectra could be recorded in solution. In the 1 H‐ and 13 C‐NMR spectra in dichloromethane solution the resonances of the α‐ and β‐positions indicate a symmetrically bridged ferrocenophane backbone consistent with a structure as in 2 .…”

“…In this vein organolead cations have been obtained via demethylation and dechlorination of respective heteroleptic Pb(II)‐compounds with electron deficient boranes. [10b], [10c] Further mono‐ and dicationic Pb(II)‐compounds have been prepared in the coordination sphere of platinum with AlCl 3 as Lewis acid, and it must be noted that in fact the number of Pb(II) tetrachloroaluminates is limited to very few examples in the literature. [10d], …”

“…[10b], [10c] Further mono‐ and dicationic Pb(II)‐compounds have been prepared in the coordination sphere of platinum with AlCl 3 as Lewis acid, and it must be noted that in fact the number of Pb(II) tetrachloroaluminates is limited to very few examples in the literature. [10d], …”

“…In fact these contacts are significantly longer than those found for the few rare examples of reported Pb(II) tetrachloroaluminates (ca. 3 Å)[10d], or the Pb ··· Cl contact of a lead β‐diketiminato cation with [ClBAr F 3 ] – anion (3.213(4) Å). [10c] Interestingly, the Pb–Cl contacts in the cationic part of 1·2 (2.719(2) to 3.016(2) Å) are longer than the ones in neutral 1 (2.644(2) ‐ 2.667(2) Å), however, quite similar to the ones in a closely related anionic chloroplumbate (2.712(2) ‐ 3.067(2) Å) .…”