Carbonyl Insertion at : The Effects of varying the Anionic Ligand X and the Neutral Ligand L

Article abstract of DOI:10.1039/DT9800000712

From the reaction of HgPh2 with cis-, the benzoyl complexes can be isolated when L = PEt3, PMe2Ph, PMePh2, PPh3, or P(C6H11)3, but when L = P(C6H4Me-o)3, AsMePh2, or AsPh3 only the complexes are formed.Metathetical replacements of the chloride ions in lead to the corresponding bromide or iodid complexes.Low temperature n.m.r. studies show that the reaction between HgPh2 and cis- gives first the carbonyl derivative , from which CO insertion proceeds.The equilibrium positions in solution between L> (each with Ph trans to L) and the binuclear benzoyl complexes are reported.The effect of X on the equilibrium position depends on the bridging ability of that group in the benzoyl dimers, stronger bridges favouring the insertion product.The neutral ligans L exert an effect by both electronic and steric factors.The magnitude of the trans influence of L directly affects the tendency of the trans phenyl group to migrate to CO, unless a critical size of L is exceeded.In these cases, the steric bulk of L favours the mononuclear carbonyl derivative.

Full text of DOI:10.1039/DT9800000712

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