Über Nickelwasserstoff, NiH
            <sub>2</sub>
            , und den Mechanismus der Hydrierung mit Nickel‐Katalysatoren

Schlenk, Wilh; Weichselfelder, Theodor

doi:10.1002/cber.19230561005

Cited by 37 publications

(4 citation statements)

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“…A definite compound, however, could not be isolated and ten years elapsed before a complex of the type (R3P)2NiHX ( 1 7 ) was preparedpractically simultaneously by Green[211 and ourselvedZ2] although by completely different routes: Green and Saito treated (16) with NaBH, while we prepared (17) by the oxidative addition of HX to an L,Ni-system (18). The product (19) of the reaction between ( 1 7 ) and AI(CH3)3 is stable at room temperature and releases methane on protonolysis with acetic acid to give (17b)["l. Treatment with ethylene effects a coupling reaction to give methane and an ethylene complex (17a).…”

Section: Stable Nickel Hydridesmentioning

confidence: 99%

The “Nickel Effect”

Fischer

Jonas

Misbach

et al. 1973

Angew. Chem. Int. Ed. Engl.

195

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Whereas the reaction of ethylene and triethylaluminum under pressure at 100°C yields trialkylaluminum compounds having long alkyl chains, the presence of small amounts of nickel salts induces the formation of butene. The discovery of this "nickel effect" represents the starting point for the development of the Ziegler catalysts. Comparatively little was formerly known about the nature and the mode of action of the catalytically active nickel species. A basis for the elucidation of the effect was provided by studies on the reduction of nickel compounds by organoaluminum compounds, on the occurrence and existence of nickel hydrides, and on interactions between nickel(0) and Lewis acids as well as organic compounds of main group metals. The most significant result of these studies is the recognition that multicenter bonding systems involving trialkylaluminum compounds and nickel atoms are involved. These react further with complex bonded ethylene in what is probably a concerted manner.

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Section: Stable Nickel Hydridesmentioning

confidence: 99%

The “Nickel Effect”

Fischer

Jonas

Misbach

et al. 1973

Angew. Chem. Int. Ed. Engl.

195

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“…The single-configurational methods include Hartree−Fock (HF), DFT with local density approximation (LDA) VWN functional V (donated as VWN5), with generalized gradient approximation (GGA) BLYP, , and with hybrid functional B3LYP , (in which VWN functional III and V 38 are used for local correlation, denoted, respectively, as B3LYP3 and B3LYP5), coupled-cluster with single and double excitations (CCSD), and CCSD with perturbative triples corrections, that is, CCSD(T) . The single-reference configuration of (I) 3 Δ g corresponds to nickel (3d δ ) 3 (3d σ ), while for (I) 1 A 1 , the lowest five a 1 , two b 1 and b 2 , and one a 2 molecular orbitals are fully occupied. The multi-configurational method used is internal-contracted multireference average quadratic single and double coupled-cluster (ic-MR-AQCC) with the active space of (12,8).…”

Section: Resultsmentioning

confidence: 99%

“…Nevertheless, although NiH 2 is the simplest triatomic nickel(II) molecule, its electronic structure is, in fact, very involved and not fully understood. In the 1920s, Schlenk and Weichselfelder , reported the existence of NiH 2 for the first time. During the past three decades, there have been some experimental and theoretical − studies on the NiH 2 molecule.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Low-Lying Electronic States of NiH₂

Zou

Boggs

2008

J. Phys. Chem. A

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The low-lying electronic states of the NiH2 molecule were investigated by using the MCQDPT2 method. In order to accurately describe the strong correlation derived from the nickel 3d9 super-configuration, a set of diffuse secondary 3d' orbitals were included in the active space, yielding a large active space of 12 electrons in 13 orbitals. It is shown that the absolute minimum energy configuration of NiH2 is bent, in agreement with the experimental observation. The global ground state is 1A1 (or A1 in the spin-orbit coupling case), whereas the lowest linear state is 3Deltag (or 3g). Some other cheaper single-configurational and multi-configurational methods were also used to study both states, and their shortcomings are discussed. Our theoretical results suggest that the arrangement of the experimental frequencies of NiH2 and NiD2 may be incorrect.

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“…In the latter the electric field of the copper ion is much stronger. It therefore seems very improbable that a hydride of nickel, NiH2, can exist, as Schlenck and Weichselfelder suppose (56). In the strong field of Ni++, Hr cannot exist and must be converted immediately into H or H2.…”

Section: The Relation Of the Two Classes Of Active Elements To The Pe...mentioning

confidence: 99%

The Mechanism of Heterogeneous Catayltic Organic Reactions. I. Catalytic Hydrogenation.

Schmidt¹

1933

Chem. Rev.

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The process of catalytic hydrogenation of organic compounds is of great interest, not only industrially but also scientifically.It comprises the hydrogenation of fatty substances, the hydrogenation of carboxides with formation of methanol, and a host of other important chemical processes. I n order to master these reactions the most important step is to understand their mechanism.I n hydrogenating fatty oils one or more double bonds between carbon atoms are converted into single bonds ; in hydrogenating carboxides one or more double bonds between carbon and oxygen atoms are reduced. This seems to be a close analogy; nevertheless the mechanism of the two processes is probably quite different, as we shall see later.We consider first the mechanism of the hydrogenation of multiple carbon bonds. For a long time I have adhered to the theory (1) that catalytic hydrogenation of multiple carbon bonds belongs to the great class of catalytic reactions that are produced by ions. I am glad now to have the opportunity of surveying the facts which seem to me to prove that ionic catalysis is involved in this type of hydrogenation.But first, what is ionic catalysis? Ostwald (2) and Arrhenius (3) were the first to find that ions 1 This is the first of a series of three articles. 11, The Dissociation of Carbon Bonds, is scheduled for publication in

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Über Nickelwasserstoff, NiH ₂ , und den Mechanismus der Hydrierung mit Nickel‐Katalysatoren

Cited by 37 publications

References 1 publication

The “Nickel Effect”

The “Nickel Effect”

Theoretical Study on Low-Lying Electronic States of NiH₂

The Mechanism of Heterogeneous Catayltic Organic Reactions. I. Catalytic Hydrogenation.

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Über Nickelwasserstoff, NiH 2 , und den Mechanismus der Hydrierung mit Nickel‐Katalysatoren

Cited by 37 publications

References 1 publication

The “Nickel Effect”

The “Nickel Effect”

Theoretical Study on Low-Lying Electronic States of NiH2

The Mechanism of Heterogeneous Catayltic Organic Reactions. I. Catalytic Hydrogenation.

Contact Info

Product

Resources

About

Über Nickelwasserstoff, NiH ₂ , und den Mechanismus der Hydrierung mit Nickel‐Katalysatoren

Theoretical Study on Low-Lying Electronic States of NiH₂