Carbonyl Complexes of Molybdenum and their Catalytic Activity

Szymańska-Buzar, Teresa

doi:10.2174/138527212798993112

Cited by 18 publications

(6 citation statements)

References 102 publications

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“…However, less attention has been paid to early transition metal-mediated ATRA reactions due to the difficulty to control the redox behavior. [26,27] Interestingly, transition metal dinuclear complexes of main group 5 (Nb and Ta), 6 (Cr, Mo and W) and 7 (Re) are more inclined to form multiple bonds between two metal centers. These compounds have been shown to display some inherent characteristics.…”

Section: Introductionmentioning

confidence: 99%

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Kang

Huo

Meng

et al. 2020

Applied Organom Chemis

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Transition metal-catalyzed atom transfer radical addition (ATRA) reactions are an effective and versatile strategy for constructing carbon-carbon bonds in organic synthesis. Typically, the metal center in this metal-assisted radical transformation undergoes a reversible redox process. In this work, a quintuply-bonded dinuclear complex, Mo 2 (N^N) 2 {N^N = μ-κ 2-CH[N(2,6-iPr 2 C 6 H 3)] 2 }, has been investigated as potential catalyst for radical addition of CCl 4 to 1-hexene by performing density functional theory (DFT) calculations. The study shows that the Mo 2 (N^N) 2-mediated radical addition reaction is computationally predicted to occur with acceptable activation energies, indicating that the Mo-Mo quintuple bond can be applied as an effective catalyst for this transformation under mild conditions. The whole reaction involves 3 steps, two of which are metal-mediated. Firstly, the C-Cl bond activiation catalyzed by Mo 2 (N^N) 2 to obtain Mo 2 (N^N) 2 Cl and •CCl 3 radical; Then the •CCl 3 radical interacts with 1-hexene to get an addition, the addition product reacts with the Mo 2 (N^N) 2 Cl to get the last product and regenerate the catalyst Mo 2 (N^N) 2. Both the thermodynamic and kinetic study show that the second step is the rate-determine step. When coordinating solvent pyridine is added to the catalytic reaction, the reaction is suppressed due to their high energies barriers, which is consistent with experimental results.

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Section: Introductionmentioning

confidence: 99%

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Kang

Huo

Meng

et al. 2020

Applied Organom Chemis

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“…Nowadays, a large number of research groups reported about the ATRA using late transition metals such as Ru, Cu, and Fe . However, early transition-metal-catalyzed ATRA reactions were less explored due to the difficulty to control the reversible redox processes . Recently, we demonstrated that the quadruply bonded dimolybdenum complexes of the Mo 2 L 4 and [ n Bu 4 N] 2 [Mo 2 L 2 Cl 4 ] (L = carboxylate, formamidinate and guanidinate) types are effective catalysts for radical addition and polymerization as well as hydrodehalogenation reactions .…”

Section: Introductionmentioning

confidence: 99%

Mixed Ligated Tris(amidinate)dimolybdenum Complexes as Catalysts for Radical Addition of CCl₄ to 1-Hexene: Leaving Ligand Lability Controls Catalyst Activity

et al. 2016

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We synthesized a series of mixed ligated tris(amidinate)dimolybdenum complexes, namely, [Mo(DAniF)(L)] [DAniF = N,N'-di(p-anisyl)formamidinate; L = acetate (OAc; 1a), m-diphenylphosphino benzoate (m-PPhBz; 1b), nicotinate (Nico; 1c), benzoate (Bz; 1d), 3-furoate (3-Furo; 1e), isonicotinate (IsoNico; 1f), and trifluoromethanesulfonate (OTf; 1g)], which served as catalysts for radical addition of CCl to 1-hexene to give 1,1,1,3-tetrachloroheptane. These mixed ligated complexes 1a-g afforded the higher yield of the radical addition product than a homoleptic DAniF complex, [Mo(DAniF)] (2). Among them, complexes 1a and 1g gave the radical addition product quantitatively after 9 h with a short induction period. When complexes 1a and 1g were treated with CCl, we detected the mixed-valence Mo(II/III) complex, [Mo(DAniF)Cl] (4), in electrospray ionization mass spectrometry measurements, indicating that the leaving nature of the L ligands was a crucial factor for initiating the catalytic reaction: the catalytic activity of the carboxylate-bridged complex 1a and the triflate-bridged complex 1g in the initial 30 min highly depended on the ligand-exchange rate of L, as estimated by monitoring the reaction with CCl in pyridine, giving the pyridine adduct complex, [Mo(DAniF)Cl(py)] (3).

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“…In order to devise similar systems, but neutral ones, we study the structure and electronic properties of similar nanoballs with either Cr or Mo, rather than Pd +2 . It is well known that these two transition metals can form neutral coordination compounds [ 29 , 30 , 31 , 32 ] and planar structures [ 33 , 34 , 35 ] that allow these nanoballs to exist.…”

Section: Introductionmentioning

confidence: 99%

Electronic Peculiarities of a Self-Assembled M12L24 Nanoball (M = Pd+2, Cr, or Mo)

et al. 2019

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We use molecular mechanics and DFT calculations to analyze the particular electronic behavior of a giant nanoball. This nanoball is a self-assembled M12L24 nanoball; with M equal to Pd+2; Cr; and Mo. These systems present an extraordinarily large cavity; similar to biological giant hollow structures. Consequently, it is possible to use these nanoballs to trap smaller species that may also become activated. Molecular orbitals, molecular hardness, and Molecular Electrostatic Potential enable us to define their potential chemical properties. Their hardness conveys that the Mo system is less reactive than the Cr system. Eigenvalues indicate that electron transfer from the system with Cr to other molecules is more favorable than from the system with Mo. Molecular Electrostatic Potential can be either positive or negative. This means that good electron donor molecules have a high possibility of reacting with positive regions of the nanoball. Each of these nanoballs can trap 12 molecules, such as CO. The nanoball that we are studying has large pores and presents electronic properties that make it an apposite target of study.

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Carbonyl Complexes of Molybdenum and their Catalytic Activity

Cited by 18 publications

References 102 publications

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Mixed Ligated Tris(amidinate)dimolybdenum Complexes as Catalysts for Radical Addition of CCl₄ to 1-Hexene: Leaving Ligand Lability Controls Catalyst Activity

Electronic Peculiarities of a Self-Assembled M12L24 Nanoball (M = Pd+2, Cr, or Mo)

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Carbonyl Complexes of Molybdenum and their Catalytic Activity

Cited by 18 publications

References 102 publications

Reaction Mechanism and Kinetics study on Addition of CCl4 to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Reaction Mechanism and Kinetics study on Addition of CCl4 to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Mixed Ligated Tris(amidinate)dimolybdenum Complexes as Catalysts for Radical Addition of CCl4 to 1-Hexene: Leaving Ligand Lability Controls Catalyst Activity

Electronic Peculiarities of a Self-Assembled M12L24 Nanoball (M = Pd+2, Cr, or Mo)

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Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Mixed Ligated Tris(amidinate)dimolybdenum Complexes as Catalysts for Radical Addition of CCl₄ to 1-Hexene: Leaving Ligand Lability Controls Catalyst Activity