Details

Autor(en) / Beteiligte

• Tho Nguyen, Minh
• Gusev, Dmitry G.
• Dmitrienko, Anton
• Pilkington, Melanie
• Nikonov, Georgii I.

Titel

Reversible Coupling of Germylone with Isocyanates

Ist Teil von

• Chemistry : a European journal, 2024-04, Vol.30 (24), p.e202400613-n/a

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Wiley Online Library Journals Frontfile Complete

Beschreibungen/Notizen

• The germylone dimNHCGe (5, dimNHC=diimino N‐heterocyclic carbene) undergoes a [2+2] cycloaddition with isocyanates RNCO (R=4‐tolyl or 3,5‐xylyl) to furnish novel alkyl carboxamido germylenes 7 (R=4‐tolyl) and 8 (R=3,5‐xylyl), featuring a C−C bond between the former carbene carbon and the isocyanate moiety. Heating a mixture of 8 with 4‐tolyl isocyanate to 100 °C results in isocyanate metathesis, demonstrating reversible C−C bond formation on the reduced germanium compound. DFT calculations suggest that this process occurs via the reductive dissociation of isocyanate from 8 that regenerates the parent Ge(0) compound 5. Ge(0) compound 5 undergoes coupling with isocyanates to afford imine‐ligated alkyl carboxamido germylenes 7 and 8. Moreover, this addition is reversible, as evidenced by an exchange reaction of 8 with p‐tolyl isocyanate and by DFT calculations.