Specific formation of isocyanide iron complexes by reaction of primary carbamoyl ferrates with oxalylchloride

Reaction of primary carbamoyl ferrates {(CO) 4Fe[C(O)NHR]} − (R=Me, Et, allyl, decyl, cyclohexyl, t-butyl, benzyl, phenyl) with 1/2 equiv. of oxalylchloride affords cis-bis-carbamoyl intermediates: (CO) 4Fe[C(O)NHR] 2 which thermally give rise, in good yields, to the mono-isocyanide complexes (CO) 4...

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Bibliographic Details
Published in:Inorganica Chimica Acta 2003-07, Vol.350, p.656-660
Main Authors: Luart, Denis, Salaün, Jean-Yves, Patinec, Véronique, Rumin, René, des Abbayes, Hervé
Format: Article
Language:English
Subjects:
Carbamoyl
Chemical Sciences
Dialkylurea
Iron
Isocyanide
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Summary:Reaction of primary carbamoyl ferrates {(CO) 4Fe[C(O)NHR]} − (R=Me, Et, allyl, decyl, cyclohexyl, t-butyl, benzyl, phenyl) with 1/2 equiv. of oxalylchloride affords cis-bis-carbamoyl intermediates: (CO) 4Fe[C(O)NHR] 2 which thermally give rise, in good yields, to the mono-isocyanide complexes (CO) 4Fe(CNR). The mechanism of the reaction is discussed. Via a similar process, an alkoxycarbamoyl intermediate (CO) 4Fe[C(O)NHR](CO 2Me) affords Fe(CO) 5 and 1,3-dialkylurea. The reaction of primary carbamoyl ferrates {(CO) 4Fe[C(O)NHR]} − with 1/2 equiv. of oxalylchloride affords, in good yields, mono-isocyanide iron complexes (CO) 4Fe(CNR). The reaction probably results from an hydrogen migration between the two carbamoyl ligands of the intermediate cis-(CO) 4Fe[C(O)NHR] 2 affording an hydroxy amino carbene intermediate whose further dehydration could give rise to the final isocyanide complex.
ISSN:0020-1693
1873-3255
0020-1693
DOI:10.1016/S0020-1693(02)01553-0