Palladium and Platinum

Hartley, F. R.

doi:10.1016/s0010-8545(00)80462-2

Cited by 29 publications

(12 citation statements)

References 354 publications

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“…Melting points were determined with a Büchi 535 capillary meting‐point apparatus. Diphenylphosphane68 and dimesylate 1 b 30 as well as [PtCl 2 (PhCN) 2 ],69 [PdCl 2 (PhCN) 2 ]69 and [PdClMe(cod)]70 were synthesised according to literature procedures. We have not provided microanalytical data for the nitrile complexes reported in this study, since these species equilibrate with either one or two other species.…”

Section: Methodsmentioning

confidence: 99%

Cyclodextrin Phosphanes as First and Second Coordination Sphere Cavitands

Engeldinger

Armspach

Matt

et al. 2003

Chemistry A European J

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The binding properties of two alpha-cyclodextrins, each containing two C(5)-linked "CH(2)PPh(2)" units, L 1 (A,D-substituted) and L 2 (A,C-substituted), have been investigated. Both ligands readily form transition-metal chelate complexes in which the metal centres are immobilised at the cavity entrance. Although diphosphane L 1 displays a marked tendency to behave only as a trans-spanning ligand, the ligand possesses a certain degree of flexibility, for example, allowing the stabilisation of a trigonal silver(I) complex in which the bite angle drops to 143 degrees. Another feature of L 1 concerns its ability to function as an hemilabile ligand. Together with four methoxy groups anchored onto the primary face, the two P(III) centres of L 1 form a circularly arranged P(2)O(4) 12-electron donor set able to complex an Ag(+) ion in a dynamic way, each of the four oxygen atoms coordinating successively to the silver ion. Furthermore, the particular structures of L 1 and L 2, characterised by the presence of P(III) units lying close to the cavity entrance, lead upon complexation to complexes whereby the first coordination sphere is partly entrapped in the cyclodextrin. Thus, when treated with metal chlorides, both ligands systematically produce complexes in which the Mbond;Cl unit is maintained inside the cyclodextrin through weak Cl.H-5 interactions. The chelate complex [Ag(L 1)]BF(4) reacts with acetonitrile in excess to afford a mixture of two equilibrating complexes, [Ag(acetonitrile)(L 1)]BF(4) and [Ag(acetonitrile)(2)(L 1)]BF(4), whose coordinated nitriles lie inside the cyclodextrin cavity. The inner-cavity ligands can be substituted by a benzonitrile molecule. The present study provides the first identification of an [Ag(acetonitrile)(2)(phosphane)(2)](+) ion. The unexpected stabilisation of this species probably rests on a cavity effect, the cyclodextrin walls favouring recombination of the complex after facile dissociation of the nitrile ligands.

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Section: Methodsmentioning

confidence: 99%

Cyclodextrin Phosphanes as First and Second Coordination Sphere Cavitands

Engeldinger

Armspach

Matt

et al. 2003

Chemistry A European J

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“…This difference can be attributed to the standard oxidation potentials for the M 0 / M II couples which are more negative for platinum than for palladium [35] and to the 10 3 times faster substitution reaction rates of Pd II compared to Pt II . [36] The structure of 6 ( Figure 6), indicated by solution state NMR spectroscopic data, was confirmed by X-ray crystallographic analysis.…”

Section: Palladium Complexesmentioning

confidence: 99%

Platinum(II) and Palladium(II) Complexes with N‐Aminoguanidine

et al. 2007

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N-Aminoguanidine (Amgu) was examined for its behaviour as a ligand for platinum(II) and palladium(II). Protonated AmguH + can coordinate platinum as a monodentate ligand bound via the N4 amino group. Deprotonated, electrically neutral Amgu forms chelate complexes with both Pt II and Pd II ; in these complexes Amgu is coordinated to the metal by the N4 amino group and the deprotonated N1 imino group, forming a five-membered ring. K[PtCl 3 (dmso)] reacted with Amgu·HCl to yield a chelate complex with N1 bound trans to S, suggesting that an exchange between the N1 and N4 binding sites followed the primary nucleophilic attack of N4

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“…Studies of palladium complexes in organic synthesis and catalytic processes, as well as studies of their chemical reactivity, spectroscopy and structural aspects have received great attention . Palladium(II) complexes possessing simple N-atom donors are well documented in the literature (Hartley, 1981) and a number of structural studies have been reported on these complexes. However, to the best of our knowl- served in (4-C1CsH4N)4Pd(CsHF602)2 (Siedle & Pignolet, 1982).…”

Section: Commentmentioning

confidence: 99%