1973 977 Organocobalt Complexes. Part II. Reaction of Acetylenehexacarbonyldicobalt Complexes, ( R1C2Ra)Co,(CO),, with Norbornene and its Derivat ives By lhsan U. Khand, Graham R. Knox, Peter L. Pauson,' William E. Watts, and (in part) Michael 1.Tetra-and hexa-hydro-4,7-methanoinden-l -ones and the analogous indacenediones (VII1)-(X) are formed stoicheiometrically by the title reaction or catalytically from acetylenes, norbornene derivatives, and carbon monoxide in the presence of octacarbonyldicobalt. The process leads stereoselectively to ketones of the exo-series and methyl or phenyl groups derived from the appropriate monosubstituted acetylenes are always found adjacent to the carbonyl group. The lH n.m.r. spectra of the products are discussed and the use of an europium shift reagent together with spin decoupling is shown to allow clear distinction of the isomeric methanoindacenediones (VIII) and (IX).
Surnmaty Reaction of bicyclo [2,2,. This must result from scission (reverse Diels-Alder alkynedicobalt hexacarbonyls in inert solvents gives reaction) of part of the norbornadiene to acetylene and dicarbonylcyclopentadienylcobalt, but in aromatic hydro-cyclopentadiene. From the known rate data for this carbons arene-nonacarbonyltetracobalt complexes are reaction' it is clear that no significant scission would occur
The addition of hydride to a series of (ha1ogenoarene)cyclopentadienyliron cations has been shown to occur exclusively a t the arene ring, with reaction at positions orfbo to the halogen substituent favoured. The bromoarene derivatives undergo partial debromination both under the conditions of their formation from ferrocene and by reaction with borohydride. The l H n.m.r. spectra of these compounds are discussed.
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