Abstract
Rate constants associated with the tertiary phosphine-induced formation of the metal acyls, [(η 5-C 5H 5)(CO)(PR 3)FeCOCH 2Cy] and [(η 5-C 5H 5)(CO) 2(PR 3)MoCOCH 2Ph], show no correlation with the electronic properties of the phosphine, but exhibit a marked dependence on steric effects. Rates decrease slightly with increase in phosphine cone angles in the lower ranges, but drop very rapidly at higher cone angles. The behaviour is consistent with the concept of a pocket of limited size around the metal centre, with large intermolecular effects arising when the sizes of the tertiary phosphine and the pocket become comparable.
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