Synthesis, Structure and Reactivity of a Cyapho(dicyano)methanide Salt.
Angew Chem Int Ed Engl
; 61(39): e202208921, 2022 Sep 26.
Article
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| MEDLINE
| ID: mdl-35876032
ABSTRACT
We describe the synthesis of a cyapho(dicyano)methanide salt, [K(18-crown-6)][C(CN)2 (CP)], from reaction of [Na(18-crown-6)][PH2 ] (18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane) with 1,1-diethoxy-2,2-dicyanoethylene (EtO)2 C=C(CN)2 . The reaction proceeds through a Michael addition-elimination pathway to afford [Na(18-crown-6)][HP{C(OEt)=C(CN)2 }]. Addition of a strong, non-nucleophilic base (KHMDS) to this intermediate results in the formation of [K(18-crown-6)][C(CN)2 (CP)]. Subsequent reactivity studies reveal that the cyapho(dicyano)methanide ion is susceptible to protonation with strong acids to afford the parent acid HC(CN)2 (CP). The reactivity of the cyaphide moiety in [C(CN)2 (CP)]- was explored through coordination to metal centers and in cycloaddition reactions with azides.
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Colección:
01-internacional
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MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2022
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Article
País de afiliación:
Reino Unido