Electron belt-to-σ-hole switch of noncovalently bound iodine(<scp>i</scp>) atoms in dithiocarbamate metal complexes

Зеленков, Лев Е.; Eliseeva, Anastasiya A.; Baykov, Sergey V.; Suslonov, Vitalii V.; Galmés, Bartomeu; Frontera, Antonio; Kukushkin, Vadim Yu.; Ivanov, Daniil M.; Bokach, Nadezhda A.

doi:10.1039/d1qi00314c

Cited by 37 publications

(48 citation statements)

References 110 publications

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“…However, recently the QTAIM approach has been combined with other approaches, such as the NCIPlot analysis. [46,49] Predominantly, XRD structure coordinates were employed for subsequent theoretical studies, [46,48,50] while in some instances the theoretical approaches used only model complexes, for example, I•••Co(I) and I•••Au(À 1). [51][52][53] In the following subsections, we inspected the appropriate geometrical parameters and computationally analyzed the XRD structures involving structure-directing σ-hole•••d[M] interactions for the occurrence of HaBs and highlighted applications of these interactions for HaB-involving crystal engineering.…”

Section: σ-Hole•••m Interactionsmentioning

confidence: 99%

“…Several examples of Pt II -involved HaBs have been found and discussed in the literature, thus demonstrating the ability of platinum(II) square-planar complexes to participate in this type of metal-involving unconventional HaB. [43,47,49,50,71,[80][81][82][83][84][85] acceptor. Agreeably, the MEP surface plot represented in Figure 10(c) demonstrates that the MEP value above and below the platinum(II) center is larger in its absolute value than that at the palladium(II) atom (Figure 8c), and thus it is more suitable as an acceptor for the occurrence of σ-hole interactions.…”

Section: Platinum(ii)mentioning

confidence: 99%

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Metal Centers as Nucleophiles: Oxymoron of Halogen Bond‐Involving Crystal Engineering

Ivanov

Bokach

Kukushkin

et al. 2021

Chemistry A European J

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This review highlights recent studies discovering unconventional halogen bonding (HaB) that involves positively charged metal centers. These centers provide their filled d-orbitals for HaB, and thus behave as nucleophilic components toward the noncovalent interaction. This role of some electron-rich transition metal centers can be considered an oxymoron in the sense that the metal is, in most cases, formally cationic; consequently, its electron donor function is unexpected. The importance of Ha•••d-[M] (Ha = halogen; M is Group 9 (Rh, Ir), 10 (Ni, Pd, Pt), or 11 (Cu, Au)) interactions in crystal engineering is emphasized by showing remarkable examples (reported and uncovered by our processing of the Cambridge Structural Database), where this Ha•••d-[M] directional interaction guides the formation of solid supramolecular assemblies of different dimensionalities.

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Section: σ-Hole•••m Interactionsmentioning

confidence: 99%

Section: Platinum(ii)mentioning

confidence: 99%

Metal Centers as Nucleophiles: Oxymoron of Halogen Bond‐Involving Crystal Engineering

Ivanov

Bokach

Kukushkin

et al. 2021

Chemistry A European J

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“…We used the equation E = 0.556*V r to estimate the association energy of each HaB. This equation has been successfully used before in a variety of halogen bonding interactions [41][42][43][44][45][46][47][48][49]. As a result, the association energy of HaB "a" is −1.67 kcal/mol, HaB "b" is −0.78, and HaB "c" is −0.88 kcal/mol.…”

Section: Dft Calculationsmentioning

confidence: 99%

On the Importance of Halogen Bonding Interactions in Two X-ray Structures Containing All Four (F, Cl, Br, I) Halogen Atoms

et al. 2021

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This manuscript reports the synthesis and X-ray characterization of two octahydro-1H-4,6-epoxycyclopenta[c]pyridin-1-one derivatives that contain the four most abundant halogen atoms (Ha) in the structure with the aim of studying the formation of Ha···Ha halogen bonding interactions. The anisotropy of electron density at the heavier halogen atoms provokes the formation of multiple Ha···Ha contacts in the solid state. That is, the heavier Ha-atoms exhibit a region of positive electrostatic potential (σ-hole) along the C–Ha bond and a belt of negative electrostatic potential (σ-lumps) around the atoms. The halogen bonding assemblies in both compounds were analyzed using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, the quantum theory of “atom-in-molecules” (QTAIM), the noncovalent interaction plot (NCIplot), and the electron localization function (ELF).

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“… 17 , 18 Further works of van Koten et al showed that the analogous palladium and nickel NCN pincer complexes interact with diiodine in other ways. 19 − 21 Nevertheless, later works represented metal-involving XB not only with Pt II 22 − 28 and Pd II 23 , 27 , 29 , 30 but also with Ni II , 27 , 31 Rh I , 32 , 33 Au I , 34 − 36 and Au 0 centers 37 − 41 as nucleophiles.…”

Section: Introductionmentioning

confidence: 99%

Studies of Nature of Uncommon Bifurcated I–I···(I–M) Metal-Involving Noncovalent Interaction in Palladium(II) and Platinum(II) Isocyanide Cocrystals

et al. 2021

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Two isostructural trans -[MI 2 (CNXyl) 2 ]·I 2 (M = Pd or Pt; CNXyl = 2,6-dimethylphenyl isocyanide) metallopolymeric cocrystals containing uncommon bifurcated iodine···(metal–iodide) contact were obtained. In addition to classical halogen bonding, single-crystal X-ray diffraction analysis revealed a rare type of metal-involved stabilizing contact in both cocrystals. The nature of the noncovalent contact was studied computationally (via DFT, electrostatic surface potential, electron localization function, quantum theory of atoms in molecules, and noncovalent interactions plot methods). Studies confirmed that the I···I halogen bond is the strongest noncovalent interaction in the systems, followed by weaker I···M interaction. The electrophilic and nucleophilic nature of atoms participating in I···M interaction was studied with ED/ESP minima analysis. In trans -[PtI 2 (CNXyl) 2 ]·I 2 cocrystal, Pt atoms act as weak nucleophiles in I···Pt interaction. In the case of trans -[PdI 2 (CNXyl) 2 ]·I 2 cocrystal, electrophilic/nucleophilic roles of Pd and I are not clear, and thus the quasimetallophilic nature of the I···Pd interaction was suggested.

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Electron belt-to-σ-hole switch of noncovalently bound iodine(i) atoms in dithiocarbamate metal complexes

Abstract: Co-crystallization of the dithiocarbamate complexes [MII(S2CNEt2)2] (M = Cu 1, Ni 2, Pd 3, Pt 4) and 1,3,5-triiodotrifluorobenzene (FIB) gives an isomorphic series of (1–4)∙2FIB co-crystals exhibiting the quadruple Cu/Ni/Pd/Pt...

Cited by 37 publications

References 110 publications

Metal Centers as Nucleophiles: Oxymoron of Halogen Bond‐Involving Crystal Engineering

Metal Centers as Nucleophiles: Oxymoron of Halogen Bond‐Involving Crystal Engineering

On the Importance of Halogen Bonding Interactions in Two X-ray Structures Containing All Four (F, Cl, Br, I) Halogen Atoms

Studies of Nature of Uncommon Bifurcated I–I···(I–M) Metal-Involving Noncovalent Interaction in Palladium(II) and Platinum(II) Isocyanide Cocrystals

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