Mechanistic Details of Nickel(0)-Assisted Oxidative Coupling of CO2 with C2H4

Pápai, Imre; Schubert, Gábor; Mayer, I.; Besenyei, Gábor; Aresta, Michele

doi:10.1021/om049496+

Cited by 95 publications

(71 citation statements)

References 50 publications

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“…It is, however, also possible to follow some dynamic processes in some detail, by investigating different points of the reaction path on the potential surface. Thus, for instance, in one of our works 53 we could detect (by computing fuzzy atoms bond orders) how the presence of a Ni atom assists in a process of forming a new C C bond by first developing a "transient" Ni C bond along the reaction path, which is then replaced by the newly formed C C one. Very instructive are the studies of Lendvay,54,55 who studied the changes of bond orders along the reaction paths of different reactions.…”

Section: Discussionmentioning

confidence: 99%

Bond order and valence indices: A personal account

2006

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Abstract:The paper accounts for the author's activity in developing bond order and valence indices since the early 80s.These indices represent an important conceptual link between the physical description of molecules as systems of electrons and nuclei and the chemical picture of molecules consisting of atoms kept together by bonds. They are also useful for a systematization and interpretation of the results obtained in the quantum chemical calculations, by permitting to extract from the wave function different pieces of information that may be assigned chemical significance. In some cases they can have some predictive power, too. Historically, the prototypes of such indices were introduced in the semiempirical quantum chemistry; the most important developments were Coulson's charge-bond order matrix in the simple Hückel theory and the Wiberg index in the CNDO framework. (Valence indices were also introduced in the semiempirical theory.) The definition of the ab initio bond order index emerged from the asymptotic term of the exchange energy component of the partitioning performed in the framework of the author's so-called "chemical Hamiltonian approach" using a "mixed" second quantization formalism for overlapping basis sets. They can also be introduced by studying the exchange part of the two-particle density (or of the second-order density matrix). Some properties of the bond order indices are discussed and the author's (until now unpublished) proof is also presented, showing the sufficient conditions under which the bond order index of a homonuclear diatomics is equal to the "chemist's bond order," i.e., the half of the difference between the number of electrons occupying bonding and antibonding orbitals. The ab initio valence indices are also introduced and discussed, and it is stressed that for correlated wave function the same "exchange only" definition of the bond order and valence indices should be used, which was introduced for the SCF case. The recent concept of the "atomic decomposition of identity" is also discussed and it is utilized for introducing bond orders and valences in the framework of the "3D analysis," when atoms are defined not by their basis orbitals but as regions of the three-dimensional (3D) physical space. Two versions of the 3D analysis are considered-the AIM (atoms in molecules)-type decomposing the space into disjunct atomic domains and the "fuzzy atoms" scheme in which there are no sharp boundaries between the atoms but they exhibit a continuous transition from one to another.

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Section: Discussionmentioning

confidence: 99%

Bond order and valence indices: A personal account

2006

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“…[4] Particularly interesting is their preparation by oxidative coupling of CO 2 and simple alkenes at the nickel centre, [5][6][7] which can be considered as the initial step of so far not realized catalytic reactions using CO 2 as a C1 building block. [8,9] Some of those complexes are valuable starting compounds in organic synthesis, for example for the preparation of carboxylic acids or their derivatives. [10][11][12] Furthermore, some nickelacycles can be used as precursors for oligo-nuclear coordination compounds of nickel.…”

Section: Introductionmentioning

confidence: 99%

Nickelacyclic Carboxylates with Pyridine‐Based Ligand Sets – From Mononuclear Complexes to Supramolecular Architectures by Hydrogen Bonding

et al. 2010

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A series of nickelacyclic carboxylates of the general formula [Ni(CH2CH2COO)(L2)] with p‐substituted pyridine ligands (2: L = 4‐picoline; 3: L = 4‐MeO2C‐C4H4N; 4: 4‐Me2N‐C4H4N) was synthesized and characterized by NMR spectroscopy. A correlation between the shift of the CH2 groups of the nickelacycle in the 1H NMR spectra and basicity of the used pyridine ligand was observed. Furthermore, amino‐substituted pyridine derivatives were used in ligand‐exchange reactions leading to supramolecular assemblies via H‐bond formation between the amino function and the carboxylate group. Depending on the ligand used, discrete dimers [5: L2 = (tBu)(Me)2Si‐aminomethylpyridine], chains [6: L2 = 2‐(aminomethyl)pyridine] or layers (7: L = 4‐H2N‐C4H4N) were observed. The molecular structures of all new compounds 2–7 were determined by X‐ray measurement.

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“…DFT calculations on the formation of nickelalactones derived from C 2 H 4 and CO 2 . Energy levels are expressed in kcal/mol [69,71] Although saturated aliphatic carboxylic acids were within reach from the corresponding nickelalactones, stoichiometric functionalizations of these metallacycles should in principle not be limited to protonolysis events. In 1986, Hoberg disclosed that the thermal decomposition of the DBUcontaining nickelacycle derived from the oxidative coupling of styrene and CO 2 led to the formation of cinnamic acid (Scheme 16) [62].…”

Section: Ligandmentioning

confidence: 99%

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Juliá‐Hernández¹,

Gaydou²,

Serrano³

et al. 2016

Topics in Current Chemistry Collections

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Abstract. The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO 2 ) as a C1 building block has recently attracted a considerable attention. Among the different alternatives in CO 2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via wasteproducing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO 2 by using cheap and available Ni or Fe catalytic species.

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Mechanistic Details of Nickel(0)-Assisted Oxidative Coupling of CO₂ with C₂H₄

Cited by 95 publications

References 50 publications

Bond order and valence indices: A personal account

Bond order and valence indices: A personal account

Nickelacyclic Carboxylates with Pyridine‐Based Ligand Sets – From Mononuclear Complexes to Supramolecular Architectures by Hydrogen Bonding

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

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