Reis, Ana Cristina Reduto dos (1991) Synthesis and reactivity of (diene)tricarbonyliron(0) and (vinylketene)tricarbonyliron(0) complexes. PhD thesis, University of Warwick.

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Abstract

As a contribution to the study of r\* -Fe(CO), complexes, a series of new (dienamidc)iricarbonyliron(O) complexes (R, R, C=CR, CH=CHCONMe, )Fe(CX))i (120) (R,=Me, R, =R, =H), (143) (R, =R, =R, =H). (144) (R, =R, =Me, R,=H). (145) (R, =H. R, =R, =Me) and (146) (R, =Me, R, =R, =H) were synthesised by the reaction of Fe,(CO), with the appropriate dienamides, obtained by standard methodology. Reaction of (120) with isobutyronitrile anion led to the isolation of 2-WA'-dimethylamide-3-isobutyroniirile-5-mcihyl-cyclopentanone (127) as a 3:1 mixture of the two stereoisomers 2a-3.50 and 2.5a-3p. Cyclopentanone formation also ocurred on reaction of (143) under similar conditions, but reaction of (144) and (146) with isobutyronitrile anion gave the C-3 addition products R, R, C=CR, CH(C(CH,), CN)CH, CONMe, (151) (R, =R,=Me, R,=H) and (152)
(R, =Me. R,=R, =H). Addition of isobutyronitrile anion to the (methylester) tricarbonyli ron(0) complexes (R, R, C=CR, CH=CHCO, Me)Fe(CO), (131) (R, =Me,
R,=R,=H) and (148) (R,=RJ=R,=H) yielded new bis(isobutyronitrile) enones
R, R, C=CCH(C(CH,), CN)CHt C(C(CH,), CN)=0 (133) (R,=Me. R.-R.-H) and
(150) (R, =R,=R, =H).

The known (vinylketene)tricarbonyliron(O) complexes
(PhCH=CHCR, =C=0)Fe(CX))J (157) (R, =Me.*Bu) and the new (vinylketene)
tricarbonyliron(O) complexes (R, CH=CHCR, =C=0)Fe(C0)I (290) (R, =
-(CH,), CH=CHj, Rj=Ph), (301) (R, =‘Bu. R, =-C(CH),CNMe,) and (308) (R, =Me, R,= -SO,lBu) were synthesised by addition of MeLi under an atmosphere of carbon monoxide to the corresponding (vinylketone)Fe(CO), complexes, which were prepared from the reaction of Fe,(CO)f with the appropriate vinylcarbonyl precursors. The reactivity of the vinylketene complexes towards inter- and intramolecular cycloaddition reactions was investigated.

Item Type:	Thesis (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Transition metals, Stereochemistry, Organometallic compounds
Official Date:	July 1991
Dates:	Date Event July 1991 UNSPECIFIED
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Thomas, S. E. (Susan E.)
Sponsors:	Junta Nacional de Investigação Científica e Tecnológica (Portugal) ; Seventh Framework Programme (European Commission)
Format of File:	pdf
Extent:	[6], 172 leaves : illustrations
Language:	eng

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