Theoretical study on interactions of N-heterocyclic carbene with the bare first-row transition metals

Zhang, Xiangfei; Sun, Min; Cao, Zexing

doi:10.1007/s00214-016-1922-9

Cited by 5 publications

(3 citation statements)

References 63 publications

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“…The PCy 3 ligand interacts with nickel mainly through σ -donation, and this Ni-PCy 3 interaction does not change significantly during the bending of the highlighted C-Ni-ligand angle, resulting in a small energy penalty for the angle distortion. For SIMes ligand, the ligand-metal interaction also includes an additional d - p back donation, 28 which is not present in the Ni–PCy 3 bond. This makes the Ni–NHC bond a partial double bond.…”

Section: Resultsmentioning

confidence: 99%

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

et al. 2017

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Nickel catalysts have shown unique ligand control of stereoselectivity in the Suzuki–Miyaura cross-coupling of boronates with benzylic pivalates and derivatives involving C(sp3)–O cleavage. The SIMes ligand produces the stereochemically inverted C–C coupling product, while the PCy3 ligand delivers the retained stereochemistry. We have explored the mechanism and origins of the ligand-controlled stereoselectivity with density functional theory (DFT) calculations. The oxidative addition determines the stereoselectivity with two competing transition states, an SN2 back-side attack type transition state that inverts the benzylic stereogenic center, and a concerted oxidative addition through a cyclic transition state which provides stereoretention. The key difference between the two transition states is the substrate-nickel-ligand angle distortion; the ligand controls the selectivity by differentiating the ease of this angle distortion. For the PCy3 ligand, the nickel-ligand interaction involves mainly σ-donation, which does not require a significant energy penalty for the angle distortion. The facile angle distortion with PCy3 ligand allows the favorable cyclic oxidative addition transition state, leading to the stereoretention. For the SIMes ligand, the extra d-p back donation from nickel to the coordinating carbene increases the rigidity of nickel-ligand bond, and the corresponding angle distortion is more difficult. This makes the concerted cyclic oxidative addition unfavorable with SIMes ligand, and the back-side SN2-type oxidative addition delivers the stereoinversion.

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Section: Resultsmentioning

confidence: 99%

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

et al. 2017

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“…Furthermore, they are also known as potent σ-donor ligands in metal transition complexes. 1 − 3 Taking this into account, the strong NHC σ-donor properties will contribute to the development of metal–NHC complexes with high chemical and thermal stability. 4 , 5 …”

Section: Introductionmentioning

confidence: 99%

“…N-Heterocyclic carbenes (NHCs), which can be considered as ligands featuring a singlet carbon donor, possess a single lone-pair orbital at the carbon atom described as carbon (II). Furthermore, they are also known as potent σ-donor ligands in metal transition complexes. − Taking this into account, the strong NHC σ-donor properties will contribute to the development of metal–NHC complexes with high chemical and thermal stability. , …”

Section: Introductionmentioning

confidence: 99%

Nature of Metal–Drug Bond in Some Antitumor Active Complexes of Coinage Metal Ions

Naderizadeh

Bayat

2020

ACS Omega

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N-Heterocyclic carbene and phosphine can be labeled as solid σ-donor ligands and can contribute to stable complexes. In addition, the constructed complex can accommodate a wide variety of applications, such as pharmaceutical products. In the light of this, a theoretical analysis was carried out on the existence of metal–drug interactions of group 11 metal ions in coordination with symmetrical unsaturated N-heterocyclic carbenes [NHC(R)(R′)] and monodentate phosphine (PR 3 ). The R substitutes on N atoms in NHC and phosphines are identical, and R′ substitutes are located on two noncarbenic carbon atoms (C4 and C5) in the heterocycle complexes. All complexes are in general formula, [Tgt → ML] {where M = Cu(I), Ag(I), Au(I), Tgt = 2,3,4,6-tetra- O -acetyl-1-thio-β- d -glucopyranoside, L= [NHC(R)(R′)], and PR 3 ; R = F, Cl, Br, H, CH 3 , C 2 H 5 , SiH 3 , 2,6-diisopropylphenyl; R′ = H and Ph} at the PBE-D3/def2-TZVP level of theory. Findings show greater tolerance for the release of drugs in the presence of Ag(I) metal ions than the other metal ions studied here. Applying natural bond orbital (NBO), atoms in molecules (AIMs), energy decomposition analysis (EDA), and extended transition-state natural orbital for chemical valence (ETS-NOCV) analysis have been researched in order to ascertain the nature of M ← S and M ← C (M ← P) bonds in the complexes. Results have shown that σ donation from S to M atoms in [Tgt → MPR 3 ] complexes is better and the π acceptor is weaker than the corresponding [Tgt → MNHC(R)(R′)] complexes.

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Chemical bonding in some anticancer NHC complexes [RʹC≡C → ML] (M=Cu (I), Ag (I), Au (I); Rʹ=C10H7 and C9NH12SO2; L=NHC (R) and P (R)3; and R=F, Cl, Br, H, CH3, SiH3, Ph)

Naderizadeh,

Bayat

2024

J IRAN CHEM SOC

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Theoretical study on interactions of N-heterocyclic carbene with the bare first-row transition metals

Cited by 5 publications

References 63 publications

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

Nature of Metal–Drug Bond in Some Antitumor Active Complexes of Coinage Metal Ions

Chemical bonding in some anticancer NHC complexes [RʹC≡C → ML] (M=Cu (I), Ag (I), Au (I); Rʹ=C10H7 and C9NH12SO2; L=NHC (R) and P (R)3; and R=F, Cl, Br, H, CH3, SiH3, Ph)

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