A new synthesis for thermolabile low-valent palladium complexes by electron transfer reactions from nickel(0) to palladium(II) compounds

Schwalbe, Matthias; Walther, Dirk; Schreer, Heike; Langer, Jens; Görls, Helmar

doi:10.1016/j.jorganchem.2006.08.015

Cited by 20 publications

(13 citation statements)

References 33 publications

(39 reference statements)

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“…58 The initially proposed adsorption models had the carbons bound essentially η 4 -atop one Pd center with unusually long Pd–C bonds (>2.5 Å c.f. ~2.16 Å in Pd(COD) 2 59 ). A later DFT study of thiophene on Pd(100) explored six adsorption geometries and found an energy minimum with the double bonds bridging three metal centers and sulfur binding a fourth metal center.…”

Section: Resultsmentioning

confidence: 99%

Dipalladium(I) Terphenyl Diphosphine Complexes as Models for Two-Site Adsorption and Activation of Organic Molecules

et al. 2013

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Well-defined models for binding of organic molecules across two metal centers are relatively rare. A paraterphenyl diphosphine was employed to support a dipalladium(I) moiety. Unlike previously reported dipalladium(I) species, the present system provides a single molecular hemisphere for binding of ligands across two metal centers, enabling the characterization and comparison of the binding of a wide variety of saturated and unsaturated organic molecules. The dipalladium(I) terphenyl diphosphine toluene-capped complex was synthesized from a dipalladium(I) hexaacetonitrile precursor in the presence of toluene. The palladium centers display interactions with the π-systems of the central ring of the terphenyl unit and that of the toluene. Exchange of toluene for anisole, 1,3-butadiene, 1,3-cyclohexadiene, thiophenes, pyrroles, or furans resulted in well-defined π-bound complexes which were studied by crystallography, nuclear magnetic resonance (NMR) spectroscopy, and density functional theory. Structural characterization shows that the interactions of the dipalladium unit with the central arene of the diphosphine does not vary significantly in this series allowing for a systematic comparison of the binding of the incoming ligands to the dipalladium moiety. Several of the complexes exhibit rare μ2-η2:η2 or μ2-η2:η1 (O or S) bridging motifs. Hydrogenation of the thiophene and benzothiophene adducts was demonstrated to proceed at room temperature. The relative binding strength of the neutral ligands was determined by competition experiments monitored by NMR spectroscopy. The relative equilibrium constants for ligand substitution span over 13 orders of magnitude. This represents the most comprehensive analysis to date of the relative binding of heterocycles and unsaturated ligands to bimetallic sites. Binding interactions were computationally studied with electrostatic potentials and molecular orbital analysis. Anionic ligands were also demonstrated to form π-bound complexes.

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Section: Resultsmentioning

confidence: 99%

Dipalladium(I) Terphenyl Diphosphine Complexes as Models for Two-Site Adsorption and Activation of Organic Molecules

et al. 2013

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“…30 The cyclometallation in Ru(bmptpphz)PdCl will influence both, the redox properties of the Pd centre and the stability and reactivity of the metal centre in all oxidation states since Pd(0) forms stable bonds to organometallic ligands. 48 (3) Moreover, also the steric shielding by the anisyl-substituents might have an impact on the catalytic performance of the Pd centre. As reported in the literature, the catalytic activity of Pd as catalytic centre in a phen coordination sphere is significantly affected by the steric influence of substituents in 2,9-position (equivalent to the 2,17-position in bmptpphz).…”

Section: Photocatalytic Hydrogen Production and Mercury Poisoningmentioning

confidence: 99%

Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium

et al. 2014

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“…The C=C bond lengths in 2 are, within error, identical to 6 ] (3 a, L= PtBu 3 , 1.366(5) ; [4] 3 b, L = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, 1.374(6) [9] ). To this end, the NMR spectra offer greater insight into bonding.…”

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confidence: 58%

“…Flack parameter 0.032 (6). Crystal data for 5: C 16 H 24 AuF 6 Sb, M = 649.07, monoclinic, a = 11.2744(11), b = 14.4437(12), c = 22.443(3) , V = 3608.5 (6) 3 , T = 100 K, space group C2/c, Z = 8, reflections measured 4005, all of which were unique and used in all calculations. The final R1 was 0.1140 and the final wR(F 2 ) was 0.2994 (all data).…”

Section: Synthesis Ofmentioning

confidence: 99%

“…The solid-state structure of 2 differs from those found in the isolobal complexes [MA C H T U N G T R E N N U N G (nbe) 3 ] (M= Ni, Pd, Pt). [3,[5][6][7] Each of these crystallises as the up-up-down isomer with essentially trigonal planar metal centers interacting with the exo faces of the nbe ligands; the Pd and Pt complexes are ostensibly coplanar, whereas one of the nbe ligands is twisted out of the trigonal plane in the Ni complex. The planarity of the olefins has been shown to maximise backbonding to the alkene, [8] an effect also observed in the substantially elongated C=C bond lengths in these structures.…”

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Synthesis, Structure and Reactivity of Stable Homoleptic Gold(I) Alkene Cations

Hooper

Green

Haddow

et al. 2009

Chemistry A European J

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The rate of absorption of hydrogen, argon, and xenon into a Type II propane clathrate hydrate has been studied. The propane hydrate is synthesized from 250‐μm ice grains, is estimated to have a porosity of 65% and has roughly the consistency of chalk. Hydrogen is rapidly absorbed by the hydrate sample and approaches the equilibrium vapor pressure in an hour before a very slow residual absorption process ensues. For an initial hydrogen pressure of 1.5 MPa, about 4.5% of the available 512 cages are occupied by hydrogen after 1 h, and 4.9% after 18 h. In contrast, for both argon and xenon significantly more gas is absorbed by the hydrate but at a much slower rate: about 5% as fast for xenon and 1% as fast for argon. We conclude that hydrogen readily diffuses through the propane hydrate microcrystal structure, while argon and xenon are probably absorbed by growing new double hydrate while consuming the propane hydrate. Although considerably higher pressures would be required to store significant quantities of hydrogen in propane hydrate, it appears that the crystal can be loaded and emptied in relatively short times. © 2010 American Institute of Chemical Engineers AIChE J, 2010

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A new synthesis for thermolabile low-valent palladium complexes by electron transfer reactions from nickel(0) to palladium(II) compounds

Cited by 20 publications

References 33 publications

Dipalladium(I) Terphenyl Diphosphine Complexes as Models for Two-Site Adsorption and Activation of Organic Molecules

Dipalladium(I) Terphenyl Diphosphine Complexes as Models for Two-Site Adsorption and Activation of Organic Molecules

Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium

Synthesis, Structure and Reactivity of Stable Homoleptic Gold(I) Alkene Cations

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