Halogen bonding between metal-bound I3− and unbound I2: the trapped I2⋯I3− intermediate in the controlled assembly of copper(<scp>i</scp>)-based polyiodides

Kinzhalov, Mikhail A.; Ivanov, Daniil M.; Shishkina, Anastasia V.; Melekhova, Anna A.; Suslonov, Vitalii V.; Frontera, Antonio; Kukushkin, Vadim Yu.; Bokach, Nadezhda A.

doi:10.1039/d2qi02634a

Cited by 7 publications

(12 citation statements)

References 78 publications

(149 reference statements)

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“…In view of our interest in the chemistry of dialkylcyanamides − and also in crystal engineering involving coinage metal complexes, − we attempted to crystallize CuI with the dialkylcyanamides NCNR 2 (R 2 = Me 2 , Et 2 , C 4 H 8 , C 5 H 10 , C 4 H 8 O) in the presence of such mixed σ-/π-hole donors as 1,4-FIB or 1,4-FBrB. Despite our repeated attempts, only experiments with the system CuI/NCNMe 2 /halo(perfluoro)arenes in MeCN gave cocrystals 1 ·1,4-FIB, 2 ·1,4-FIB, and 1 ·1,4-FBrB; they all were studied by XRD.…”

Section: Resultsmentioning

confidence: 99%

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu₄I₄ Clusters

Toikka

Старова

Suslonov

et al. 2023

Crystal Growth & Design

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Cocrystallization of CuI with NCNMe2 in the presence of 1,4-diiodotetrafluorobenzene (1,4-FIB) and 1,4-dibromotetrafluorobenzene (1,4-FBrB) in MeCN gave cocrystals [Cu4I4(NCNMe2)4]·1,4-FIB, [Cu4I4(NCNMe2)2(NCMe)2]·1,4-FIB, and [Cu4I4(NCNMe2)4]·1,4-FBrB, whose solid-state structures were studied by X-ray diffraction. In these three cases, the perfluorinated haloarenes function as combined σ- and π-hole donors, and their crystal structures exhibit intermolecular contacts, including halogen bonding (HaB) and π-hole interactions with the iodine ligands of the copper clusters. Analysis of the theoretical calculation data indicated that the formation of (cubane)·(perfluorinated haloarene) π–hole dimer is slightly energetically more favorable than (cubane)·(perfluorinated haloarene) HaB-based σ-hole dimer. The π-hole contacts and HaBs are accompanied by additional hydrogen bonding and also π-hole(NCN)···X (X = Br, I) contacts. Altogether, these interactions lead to the occurrence of moderately strong noncovalent binding between copper clusters and the aromatic HaB donors.

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Section: Resultsmentioning

confidence: 99%

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu₄I₄ Clusters

Toikka

Старова

Suslonov

et al. 2023

Crystal Growth & Design

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“…Although strong π-back-donating isocyanide ligands similar to other complexes of low-oxidation state metal centers are able to stabilize the copper(I) oxidation state, (RNC)Cu I -based polyhalides are still little explored. We recently obtained the polyhalide adducts [Cu(I 3 )(CNXyl) 3 ], [Cu(I 3 )(CNXyl) 3 ]· 1 / 2 I 2 , and [Cu(CNXyl) 3 ](I 5 ) from [CuI(CNXyl) 3 ] and I 2 ; these species are formed depending on the molar ratio between the reactants . In view of our interest in isocyanide chemistry (for review, see ref ; for recent works, see refs and and references therein), copper(I) chemistry, and the supramolecular chemistry of polyhalides (for recent works, see refs , , and ), the idea of a study that combines all three areas seemed to be attractive.…”

Section: Resultsmentioning

confidence: 99%

Triiodide-Based Chair-Like Copper Complex Assembled by Halogen Bonding

Kinzhalov,

Kinzhalova,

Karnoukhova

et al. 2023

Inorg. Chem.

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Cocrystallization of the dimeric [Cu 2 (μ-I) 2 (CNXyl) 4 ] (Xyl = 2,6-Me 2 C 6 H 3 , 1) and polymeric catena-[Cu(μ-I)(CNC 6 H 3 -2-Cl-6-Me) 2 ] (2) complexes with I 2 at different molar ratios between the reactants resulted in a series of (RNC) 2 CuI-based crystal polyiodides formed along with gradual accumulation of iodine, namely the cocrystals [1The polyiodide 5•2I 2 exhibits a novel supramolecular motif�a purely inorganic halogen-bonded Cu 2 (μ 1,3 -I 3 ) 2 core in the chair conformation. The X-ray structure of 5•2I 2 featuring I•••I contacts was analyzed by a set of theoretical methods and attributed to moderately strong halogen bonding (from −3.2 to −3.9 kcal/mol); these interactions determine the supramolecular architecture of 5•2I 2 .

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“…In line with our general interest to noncovalent interactions and in particular toward metal-involving interactions (for recent reports, see refs − and references therein), we studied self-association of thiocyanate Pd II ( 3 ) and Pt II ( 4 ) complexes (Scheme ). We found that 3 and 4 form isomorphous crystals, where these metal species are assembled in 1D supramolecular polymer primarily by M···S noncovalent interactions.…”

Section: Introductionmentioning

confidence: 99%

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Kashina

Kinzhalov

Tupikina

et al. 2023

Crystal Growth & Design

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Analysis of X-ray crystal structures of newly prepared thiocyanate PdII and PtII complexes revealed the bifurcated (M–N)···S contacts in which angles ∠M···SC are close to 180°. All M···SCN–M′ noncovalent interactionsidentified in this study and also those found on the Cambridge Structural Database searchwere systematized as linear (approximately 180°) and bent (∠M···SC 80–120°). Results of appropriate theoretical study indicate that, although the linear configuration of the PdII and PtII structures is primarily determined by crystal packing effects, the attractive M···S forces are far from negligible and the linear structures correspond to the energy minimum. Furthermore, the linear arrangement is mostly determined by orbital interactions, while the bent configuration by electrostatic forces. Molecular electrostatic potential (MEP) surfaces along with the quantum theory of “atoms-in-molecules” (QTAIM) and the noncovalent interaction plot index (NCIPlot) computational tools were used to characterize the bifurcated (M–N)···S interactions. The nature of the noncovalent M···SCN–M′ forces in the PdII and PtII structures was established by NBO analysis: in both cases, the predominant donor–acceptor orbital interactions include the charge transfer from lone pair orbitals located at the M atom to the σ*-orbital of the S–C bond of a thiocyanate ligand from a neighboring complex.

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Halogen bonding between metal-bound I₃⁻ and unbound I₂: the trapped I₂⋯I₃⁻ intermediate in the controlled assembly of copper(i)-based polyiodides

Abstract: Crystallization of [CuI(CNXyl)3] (1) with I2 (exhibiting strong halogen bond donor properties), at different molar ratios between the reactants, resulted in a series of (XylNC)CuI crystal polyiodides formed along with...

Cited by 7 publications

References 78 publications

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu₄I₄ Clusters

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu₄I₄ Clusters

Triiodide-Based Chair-Like Copper Complex Assembled by Halogen Bonding

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

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Halogen bonding between metal-bound I3− and unbound I2: the trapped I2⋯I3− intermediate in the controlled assembly of copper(i)-based polyiodides

Abstract: Crystallization of [CuI(CNXyl)3] (1) with I2 (exhibiting strong halogen bond donor properties), at different molar ratios between the reactants, resulted in a series of (XylNC)CuI crystal polyiodides formed along with...

Cited by 7 publications

References 78 publications

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu4I4 Clusters

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu4I4 Clusters

Triiodide-Based Chair-Like Copper Complex Assembled by Halogen Bonding

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

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Halogen bonding between metal-bound I₃⁻ and unbound I₂: the trapped I₂⋯I₃⁻ intermediate in the controlled assembly of copper(i)-based polyiodides

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu₄I₄ Clusters

Combined σ- and π-Hole Donor Properties of Perfluorinated Iodo(or bromo)benzenes: Halogen Bonding and π-Hole Interactions in Cocrystals Including Cu₄I₄ Clusters