Group-10 π-hole⋯dz2[MII] interactions: a theoretical study of model systems inspired by CSD structures

Calabrese, Miriam; Piña, Sergi Burguera; Resnati, Giuseppe; Frontera, Antonio

doi:10.1039/d3dt00698k

Cited by 4 publications

(3 citation statements)

References 46 publications

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“…The MEP value at the metal is slightly less negative for Ni, in line with the smaller d-orbital nucleophilicity of this element. 47 Four equivalent MEP minima are located along the bisectors of the NC–M–CN angles in the molecular plane (marked by an asterisk in Fig. 8), with energies that range from −184.5 to −190.1 kcal mol −1 .…”

Section: Resultsmentioning

confidence: 99%

Interplay of a nitro group and metal ions: from coordinative binding to noncovalent semicoordination

Suslonov,

Soldatova,

Ivanov

et al. 2024

Inorg. Chem. Front.

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Section: Resultsmentioning

confidence: 99%

Interplay of a nitro group and metal ions: from coordinative binding to noncovalent semicoordination

Suslonov,

Soldatova,

Ivanov

et al. 2024

Inorg. Chem. Front.

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“…8 ), π-bond(s) 8 systems (e.g., aromatic rings), and nucleophilic metal sites (e.g., a d z 2 -nucleophilic Pt II site). 33,34 The most common group of HaB acceptors is represented by nitrogen-based nucleophiles 35 featuring sp 3 -N (amines), sp 2 -N (nitrogen heterocycles and imines), and sp-N sites. The former two groups exhibit a pronounced nucleophilicity, and it is not unusual that they are often employed as acceptor components in HaB-involving crystal engineering.…”

Section: Introductionmentioning

confidence: 99%

Push–Pull and Conventional Nitriles as Halogen Bond Acceptors in Their Cocrystals with Iodo-Substituted Perfluorobenzenes

Toikka,

Gomila,

Frontera

et al. 2023

Crystal Growth & Design

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FIB), which were studied by single-crystal X-ray diffractometry (XRD). The structure-directing I•••sp-N nitrile halogen bond (HaB) in all cocrystals was identified based on the consideration of the XRD geometrical (bond length and angles) parameters and also by Hirshfeld surface analysis, whereupon the observed HaBs were analyzed theoretically. The HaB-accepting role of the push−pulling dialkylcyanamides NCNR 2 and conventional nitriles NCR (R = Alk) was examined and compared in detail using, as model examples, the structures of cocrystals 3•1/ 2(1,4-FIB) (this work) and AdCN•1/2(1,4-FIB) (CSD refcode: KIHROL). These two cocrystals, which display similar supramolecular organization, were studied by several quantum chemistry methods including molecular electrostatic potential surface analysis, the natural bond orbital analysis, the quantum theory of atoms in molecules combined with the NCIPlot approach, and also by the Kitaura−Morokuma energy decomposition approach. While AdCN is a slightly poorer sp-N electron donor than the push− pull nitrile 3, HaBs in the cocrystals exhibit similar interaction energies. Although in the covalent chemistry the two types of nitriles often exhibit strikingly different reactivity patterns, the σ-hole-based I•••sp-N nitrile noncovalent interaction provided the leveling effect, resulting in significant similarities between the HaB situations for both nitrile species.

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“…Recently, we studied the possible capacity of these group 10 elements to act as electron donors, having a π-acidic molecule acting as electron acceptor [18][19][20][21], based on crystal structures deposited in the Cambridge Structural Database (CSD) [22]. This interaction could be explained due to the π-hole nature of the acceptor and a filled d z2 orbital of the metal in square planar complexes.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Nucleophilicity and Electrophilicity of Group 10 Elements through Substituent Effects: A DFT Study

Burguera,

Bauzá,

Frontera

2023

IJMS

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In this study, a series of electron donor (–NH2, –NMe2 and –tBu) and electron-withdrawing substituents (–F, –CN and –NO2) were used to tune the nucleophilicity or electrophilicity of a series of square planar Ni2+, Pd2+ and Pt2+ malonate coordination complexes towards a pentafluoroiodobenzene and a pyridine molecule. In addition, Bader’s theory of atoms in molecules (AIM), noncovalent interaction plot (NCIplot), molecular electrostatic potential (MEP) surface and natural bond orbital (NBO) analyses at the PBE0-D3/def2-TZVP level of theory were carried out to characterize and discriminate the role of the metal atom in the noncovalent complexes studied herein. We hope that the results reported herein may serve to expand the current knowledge regarding these metals in the fields of crystal engineering and supramolecular chemistry.

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Group-10 π-hole⋯d_z²[M^II] interactions: a theoretical study of model systems inspired by CSD structures

Abstract: In recent years Pd(II) and Pt(II) cases have been reported wherein metals in square planar complexes were used as nucleophilic partners to construct supramolecular assemblies with electrophilic molecules like σ-hole...

Cited by 4 publications

References 46 publications

Interplay of a nitro group and metal ions: from coordinative binding to noncovalent semicoordination

Interplay of a nitro group and metal ions: from coordinative binding to noncovalent semicoordination

Push–Pull and Conventional Nitriles as Halogen Bond Acceptors in Their Cocrystals with Iodo-Substituted Perfluorobenzenes

Tuning the Nucleophilicity and Electrophilicity of Group 10 Elements through Substituent Effects: A DFT Study

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