Molecular structures and proton magnetic resonance spectra of ethylene complexes of nickel and platinum

Cheng, Pei‐Tak; Cook, Christopher David; Nyburg, S. C.; Wan, Kang

doi:10.1021/ic50104a024

Cited by 96 publications

(26 citation statements)

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“…i This calculation employed a deformed free ethene molecule with the pyramidalization and C−C−H angles frozen to correspond to the calculated structures of the tricyclic alkenes. j From refs and ; average of X-ray structure values. k Gas-phase value from refs and ; error in this value is quoted as ±18 kJ mol -1 .…”

Section: Theoretical Methodsmentioning

confidence: 99%

Nature of the Metal−Alkene Bond in Platinum Complexes of Strained Olefins

et al. 1999

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Density functional theory and high-level ab initio molecular orbital methods have been used to investigate complexes of platinum with highly pyramidalized olefins: Pt(PH3)2(R) with R = C11H16, C10H14, C9H12, and C8H10. Geometries and binding energies are reported and compared to experimental values where available. Charge decomposition analyses have been carried out for all complexes, and they show a beautiful increase in olefin←Pt back-donation as the olefin becomes more pyramidal. Natural bond orbital analyses show a corresponding increase in the platinum 6s and carbon 2s character in the Pt−C bond orbital, in agreement with previous NMR studies. We also find that the binding energies of all the complexes correlate well with the olefin strain energies calculated for the free olefins.

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Section: Theoretical Methodsmentioning

confidence: 99%

Nature of the Metal−Alkene Bond in Platinum Complexes of Strained Olefins

et al. 1999

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“…Taking advantage from the peculiar steric characteristics of the tetramethyl-ethene-tetracarboxylate (tmetc) the olefin exchange equilibria were also studied from the kinetic point of view [26,31,32,34,39,43,[63][64][65]. It has been shown that the rates of exchange are strongly dependent on the steric requirement of the ancillary ligand and the mechanism is associative in nature.…”

Section: Olefin Exchangementioning

confidence: 99%

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

Canovese

Visentin

2010

Inorganica Chimica Acta

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a b s t r a c tAn overview of the general features of electron-poor olefin stabilized palladium(0) complexes bearing labile and hemi-labile ancillary ligands is presented. In particular, we have summarized the synthetic methodologies, the ligands commonly used, and the characterization of such complexes. The behavior of these species in solution is also described with particular attention to their fluxional rearrangements and reactivity. Thus, olefin exchange reactions are described and a comprehensive order of coordinative capability of the most widely used electron-poor alkenes is presented. The reactions of the title complexes dealing with olefin isomerization, oxidative addition, and formation of palladacyclopentadiene derivatives are eventually reported together with their main structural characteristics.

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“…(PPh,),-PtC2(CN), (2), (PPh,),PtC,Cl, (3), and (PPh,),-NiC2H4 (4). In order to make a critical appraisal of the D-C-D model and to learn the role played by the electron-withdrawing groups -CN and -C1 we have undertaken a threedimensional X-ray analysis of the ethylene complex (PPh,),PtC2H4, a brief report on which has already been published (5).…”

Section: Introductionmentioning

confidence: 99%

The Crystal and Molecular Structure of bis(triphenylphosphine)-(ethylene)platinum, (PPh₃)₂PtC₂H₄

Cheng¹,

Nyburg²

1972

Can. J. Chem.

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The X-ray crystal structure analysis of the triphenyl-phosphine platinum ethylene complex (PPh3),PtC,H4 is reported. The crystals belong to the monoclinic system a = 16.46(3), b = 10.85(2), c = 17.85(3) A, fi = 100.5(1)", space group P2,/a, Z = 4 molecules per cell.The ethylene C--C distance of 1.434 (13) A is in accord with that found when other transition elements form metallo-cyclopropanes. The structure has been refined by anisotropic full-matrix least-squares, the final R-factor being 0.043 for 4174 observed reflections.On rapporte l'analyse par rayons-x de la structure cristalline du complexe triphenylphosphine ethylene platine, (PPh ),PtC2H4. Les cristaux appartiennent au systeme monoclinique a = 16.46(3), b = 10.85(2), r = 17.85(3) 1, fi = 10.05(1)", au groupe spatial P2,/a, Z = 4 moltcules par maille.La distance C--C dans I'tthylene de 1.434(13) A est concordante avec celle qu'on trouve quand d'autres Clements de transition foment des m6tallo-cyclopropanes. La structure a kte raffinte par la methode anisotropique matricielle des moindres carres, le facteur R final itant de 0.043 pour les reflexions 4174 observees.

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Molecular structures and proton magnetic resonance spectra of ethylene complexes of nickel and platinum

Cited by 96 publications

References 2 publications

Nature of the Metal−Alkene Bond in Platinum Complexes of Strained Olefins

Nature of the Metal−Alkene Bond in Platinum Complexes of Strained Olefins

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

The Crystal and Molecular Structure of bis(triphenylphosphine)-(ethylene)platinum, (PPh₃)₂PtC₂H₄

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Molecular structures and proton magnetic resonance spectra of ethylene complexes of nickel and platinum

Cited by 96 publications

References 2 publications

Nature of the Metal−Alkene Bond in Platinum Complexes of Strained Olefins

Nature of the Metal−Alkene Bond in Platinum Complexes of Strained Olefins

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

The Crystal and Molecular Structure of bis(triphenylphosphine)-(ethylene)platinum, (PPh3)2PtC2H4

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The Crystal and Molecular Structure of bis(triphenylphosphine)-(ethylene)platinum, (PPh₃)₂PtC₂H₄