71806-69-4

Upstream product

• 18421-49-3 trans-Pt(phenyl)Cl(triphenylphosphine)2 
• 103712-62-5 Pt₂Cl₂(C₆H₅)2(P(C₆H₅)3)2 
• 22585-09-7 cis-triphenylphosphinecarbonylplatinum(II) dichloride 
• 587-85-9 diphenylmercury(II) 
• 71600-64-1 PtClC₆H₅COP(C₆H₅)3 
• 71600-64-1 PtClC₆H₅COP(C₆H₅)3 

Downstream Products

• 71806-69-4 [PtCl(C₆H₅)(CO)(C₆H₅)3P] 

Relevant academic research and scientific papers

Carbonylation of . New Intermediates in the CO Insertion Sequence

Phosphorus-31 n.m.r. studies of the reaction of trans- with carbon monoxide have led to the identification of several new intermediates and reaction pathways involved in the CO insertion process to produce trans-.Carbonyl addition forms a metastable five-co-ordinate compound in non-polar solvents, which eliminates a halide to form ionic species trans-X in polar solvents.Loss of PR3 from five-co-ordinate intermediates produces two isomers of which convert to the remaining isomer with Ph trans to PR3 before migration of Ph proceeds to form a benzoyl complex.A direct carbonyl insertion route from a five-co-ordinate intermediate also operates, independently of the phosphine elimination pathways, and this becomes the predominant pathways with more nucleophilic PR3 ligands.The use of elemental sulphur to remove PR3 from the reaction mixtures was instrumental in identifying some intermediates, and this method has potential synthetic value in replacing PR3 by weaker ligands at platinum.

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

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.