60772-01-2Relevant academic research and scientific papers
A multinuclear NMR study of asymmetrically coordinated η3-allyls in [PtCl(η3-allyl)(phosphine)] and [Pt(phenyl)(η3-allyl)(phosphine)] complexes
Clark, Howard C.,Hampden-Smith, Mark J.,Ruegger, Heinz
, p. 2085 - 2093 (2008/10/08)
The title complexes were prepared and fully characterized by multinuclear (1H, 31P, 13C, 195Pt) NMR methods. The 1H NMR resonances of the allyl groups were unequivocally assigned by using a combination of one- and two-dimensional NMR spectroscopic techniques. The spectroscopic data have been interpreted in terms of contributions of asymmetric η1-η2-allyl bonding modes to the more familiar symmetrical η3-allyl arrangement. The relative orientation and extent of the asymmetric η1-η2-bonding were shown to be markedly dependent upon the nature of the other ligands coordinated to platinum. On prolonged standing in chloroform solution, the title complexes rearranged to give the known complexes [X(R3P)Pt(μ-Cl)]2 and trans-XClPt(PR3)2 (X = Cl, Ph). Conversion of the allyl moiety to propene gas was shown by 1H NMR and gas chromatographic analysis.
ORGANIC GROUP TRANSFER REACTIONS BETWEEN PLATINUM(II) AND MERCURY(II)
Cross, Ronald J.,McLennan, Alistair J.
, p. 113 - 122 (2007/10/02)
Both C5H5Tl and Hg(C5H5)2 react with CR)(CO)L> (L is tertiary phosphine, Cl trans to L) to produce CR)(CO)L> (CCR trans to CO).C5H5Tl and similarly produce one isomer only (Ph trans to CO) of .Thes
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.
Reactivity of platinum diolefin complexes. Roles of trans influence and chelate effect
Anderson,Clark,Davies
, p. 1636 - 1639 (2008/10/08)
The complex [PtCl2(cod)] (cod = 1,5-cyclooctadiene) reacts with CO and tertiary phosphine to produce cis-[PtCl2(CO)L] (L = PEt3, P-n-Bu3, PMePh2, PPh3, P(C6H4F-p)
Carbonylation of . New Intermediates in the CO Insertion Sequence
Anderson, Gordon K.,Cross, Ronald J.
, p. 1434 - 1438 (2007/10/02)
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.
