Rae Victor

Reactions of dicyclopropylacetylene with iron carbonyls

Abstract Dicyclopropylacetylene has been brought into reaction under photolytic conditions with Fe(CO) 5 and under thermal conditions with Fe 2 (CO) 9 and with Fe 3 (CO) 12 . It was possible to obtain primarily monoacetylene adducts or bis(acetylene) adducts by modification of the reaction conditions. In addition to products normally obtained from reactions of acetylenes with iron carbonyls, products derived from cyclopropane ring opening were important. Of particular interest are products which resulted from ring opening and carbonyl insertion to yield cyclopentenone derivatives. Experiments were attempted to show the interrelationships between the various products obtained.

The synthesis of hexacyclopropylbenzene via cyclotrimerization of dicyclopropylacetylene by Fe3(CO)12

Di-cyclopropyl-acetylen (I) reagiert in Gegenwart von Trieisen-dodecacarbonyl (II) zum Hexakis-cyclopropyl-benzol (III) neben dem Tetrakis-cyclopropylcyclopentadienon (IV) und zwei weiteren Eisen-Komplexen (V) und (VI).

Photoreaction of o-quinodimethanetricarbonyliron with pentacarbonyliron

Abstract Irradiation of ( tetrahapio-o -quinodimethane)tricarbonyliron in the presence of Fe(CO) 5 gives three isomeric C 8 H 8 Fe 2 (CO) 6 complexes.

Butatriene-hexacarbonyldiiron complexes via dehydroxylation of unsaturated diols by Fe(CO)1

Abstract Butatriene-diiron hexacarbonyl complexes have been prepared simply and in good yield from thermal reaction of Fe(CO)1 with -butynediols or ,-diiodo--butene-1,4-diols. Geometric isomers of these complexes are usually obtained where such isomerisation is possible. Another product of reaction, derived from loss of HOH from the butynediol, is described.

Trends in electron-impact fragmentation of substituted styrenebis(tricarbonyliron) complexes induced by the metal and substitution

Abstract A study of electron-impact induced processes of thirty substituted styrenebis(tricarbonyliron) complexes XC 6 H 4 C(R α )=CR β [Fe(CO) 3 ] 2 , and of some ten corresponding styrene free ligands is described. All the mass spectra of the organoiron complexes are characterized by the consecutive losses of carbon monoxide followed by loss of one or tow iron atoms: [LFe 2 (CO) 6 ] +. (a) LFe +. 2 (c) LFe +. (g) L + Depending on the nature of the substituent, X, and its position on the styrene ligand, the organic moiety in LFe + ruptures in four main modes: ( d ) loss of neutral methane when X = H, CH 3 , C 6 H 5 , CH 3 O and F; R α = CH 3 and R β = H; ( e ) loss of neutral acetylene when X = H, CH 3 O; R α = H and R β = CH 3 ; ( f ) loss of HX when X = halogen, R α = H, CH 3 and R β = H; ( g ) loss of iron. In the halogen-containing organoiron complexes, the ionic fragment LFe +. 2 predominates in the mass spectra. It is characterized by its tendency to lose a neutral alkyne molecule to yield the corresponding ionic fragment of diiron—halogenobenzene [mode ( b )]. Unlike the organoiron complexes which eject neutral molecules, the corresponding free ligands tend to lose mainly radical species. The preparation and properties of nine hitherto unreported styrene—bis(tricarbonyliron) complexes are described.

Photoreactions of a methylene-spirane and dispirane with Fe(CO)5. σ,π-Complex formation from a double cyclopropane rearrangement

The major product from the photoreaction of 4-methylenedispiro[2,1,2,3]decane (5) with Fe(CO)5 is shown to be a tricarbonyliron σ,π-complex of structure (7), whereas the products from 4-methylenespiro[2,4]heptane (9) and 4-methylenespiro[2,5]octane (15) are the respective bi-cyclic enones (12)–(13) and (16).

Photoreaction of benzocyclobutadienetricarbonyliron with pentacarbonyliron

Irradiation of 1—2a(6a)-η-benzocyclobutadienetricarbonyliron (5) in the presence of Fe(CO)5 gives a mixture of 1—2a(6a)-η : 3-6-η-benzocyclobutadienebistricarbonyliron (6), 1—3a(7a)-η-ferraindenebistricarbonyiiron (3) 1—3a(7a)-η : 4–7-η-ferraindenebistricarbonyliron (4). 1–3a(7a)-η-ferra-2H-indenetricarbonyliron (7), and 1–3a(7a)-η-ferra-2H-indenetricarbonyliron (8); complex (6) is formed via diene-type co-ordination of the four ring π-electrons in (5), while complexes (3), (4) and (7), (8) result from cyclobutadiene ring opening and insertion of an Fe(CO)3 unit.