REACTION OF FISCHER TYPE CHROMIUM CARBENE COMPLEXES WITH N,N-DIMETHYLFORMAMIDE DIALKYL ACETALS (DMF-DAA) - AN UNEXPECTED CARBON-CARBON BOND BREAKING (Articolo in rivista)

Type
Label
  • REACTION OF FISCHER TYPE CHROMIUM CARBENE COMPLEXES WITH N,N-DIMETHYLFORMAMIDE DIALKYL ACETALS (DMF-DAA) - AN UNEXPECTED CARBON-CARBON BOND BREAKING (Articolo in rivista) (literal)
Anno
  • 1993-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/om00032a023 (literal)
Alternative label
  • BALDOLI, C; LATTUADA, L; LICANDRO, E; MAIORANA, S; PAPAGNI, A (1993)
    REACTION OF FISCHER TYPE CHROMIUM CARBENE COMPLEXES WITH N,N-DIMETHYLFORMAMIDE DIALKYL ACETALS (DMF-DAA) - AN UNEXPECTED CARBON-CARBON BOND BREAKING
    in Organometallics
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • BALDOLI, C; LATTUADA, L; LICANDRO, E; MAIORANA, S; PAPAGNI, A (literal)
Pagina inizio
  • 2994 (literal)
Pagina fine
  • 3000 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 12 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 7 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 8 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Consiglio Nazionale delle Ricerche; Università degli Studi di Milano (literal)
Titolo
  • REACTION OF FISCHER TYPE CHROMIUM CARBENE COMPLEXES WITH N,N-DIMETHYLFORMAMIDE DIALKYL ACETALS (DMF-DAA) - AN UNEXPECTED CARBON-CARBON BOND BREAKING (literal)
Abstract
  • A series of pentacarbonyl(2-oxacyclopentylidene)chromium (5a-f) were reacted with NN-dimethylformamide dimethyl acetal (DMF-DMA), resulting in the pentacarbonyl(2-oxa-5-[(N,N-dimethylamino)methylidene]cyclopentylidene)chromium (6a-f) and the unexpected pentacarbonyl(2-oxa-5-(cyclopropylmethylidene)cyclopentylidene)chromium (7a-d). Open chain Fischer type carbene complexes (CO)5Cr=C(OCH3)CH2R, (1a-d) also react easily with DMF-DAA (2a-d). When R1 = H, the carbene complex (CO)5Cr=C(OCH3)CH=CHN(CH3)2 is formed in high yield; however, when R1 = alkyl, the reaction products are dialkoxy complexes (CO)5Cr=C(OCH3)OR2 (4a-d), in which the OR2 group comes from the DMF-DAA. The mechanisms of the above reactions are elucidated. The cyclopropyl ring present on compounds 7a-d arises from a contraction of the five membered ring of complexes 5a-d due to the breaking of the bond between the carbene carbon atom and the a-carbon atom. The same mechanism explains the formation of dialkoxy complexes 4a-d from complexes 1b-d. In the case of the reaction of the complex (CO)5Cr=C(OCH3)CH2CH2CH2CH3 (1d) with N,N-dimethylformamide dineopentyl acetal (2d), the intermediary formation of an enamine derivative has been demonstrated. Moreover the reaction of pentacarbonyl(2-oxa-4,4-dimethylcyclopentylidene)chromium (5g) with DMF-DMA (2a) allowed the isolation of 2,2-dimethylcyclopropanecarbaldehyde (characterized as the (2,4-dinitrophenyl)hydrazone). (literal)
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