78147-53-2Relevant academic research and scientific papers
Reactivity of platinum diolefin complexes. 2. Reactions with bulky and chelating group 5B ligands and studies relating to carbonyl insertion
Anderson,Clark,Davies
, p. 3607 - 3611 (2008/10/08)
Reactions of [PtXY(cod)] (X = Y = Cl, Me, Ph; X = Cl, Y = Ph, COPh) with bulky monodentate and chelating group 5B ligands have been examined by 31P{1H} NMR spectroscopy. The molecularity of the products is a function of steric bulk with monodentate ligands and a function of chelate bite with bidentate ligands. The geometry of the products is controlled largely by the trans influence of both neutral and anionic groups. Where the steric constraints involved in nucleophilic attack of the complexes by bulky ligands are dominant, olefin displacement can be prevented entirely. Reactions of [PtXYL2] (X = Y = Ph, Cl; X = Ph, Y = Cl; L = monodentate ligand, L2 = bidentate ligand) with carbon monoxide have been studied by 31P{1H} and 13C{1H} NMR and infrared spectroscopies. The mechanism of carbonyl insertion at platinum(II) is discussed in terms of the chelate effect and the trans influence of the anionic ligands.
Carbonyl Insertion at : The Effects of varying the Anionic Ligand X and the Neutral Ligand L
Anderson, Gordon K.,Cross, Ronald J.
, p. 712 - 715 (2007/10/02)
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.
