TY - JOUR

T1 - Halogen Bonding between Metal-bound I3– and Unbound I2: The Trapped I2···I3– Intermediate in the Controlled Assembly of Copper(I)-based Polyiodides

AU - Кинжалов, Михаил Андреевич

AU - Иванов, Даниил Михайлович

AU - Шишкина, Анастасия

AU - Мелехова, Анна Андреевна

AU - Суслонов, Виталий Валерьевич

AU - Frontera, Antonio

AU - Кукушкин, Вадим Юрьевич

AU - Бокач, Надежда Арсеньевна

PY - 2023/1/11

Y1 - 2023/1/11

N2 - The identification of halogen bonded-intermediates is key to understanding the precise mechanism for the generation of I 5 − (and I 8 2− ) ligands from I 2 and metal-coordinated I 3 − . Crystallization of [CuI(CNXyl) 3 ] (1) with I 2 (exhibiting strong halogen bond donor properties), at different molar ratios between the reactants, resulted in a series of (XylNC)Cu I crystal polyiodides formed along with gradual accumulation of iodine, namely [Cu(I 3 )(CNXyl) 3 ] (two crystalline polymorphs 2 I and 2 II ), [Cu(I 3 )(CNXyl) 3 ]·½I 2 (2·½I 2 ) and [Cu(CNXyl) 3 ](I 5 ) (3); all these compounds were studied by X-ray diffractometry. Molecular electrostatic potential (MEP) surface plots were also calculated using density functional theory (DFT) for isolated molecules of 2 and I 2 , showing electrophilic and nucleophilic sites. Halogen bonding in 2·½I 2 was additionally elucidated for both crystal and cluster models, including combined quantum theory of atoms-in-molecules (QTAIM) and one-electron potential (OEP) projections. For model clusters, DFT energetic analysis, quantum theory of atoms-in-molecules, combined with the noncovalent interaction index plot (QTAIM/NCIplot), natural bond orbital (NBO) donor–acceptor charge transfer analysis, and Wiberg bond index (WBI) analysis were used. In the structure of 2·½I 2 , the presence of an I 2 ⋯I 3 − halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I 5 − (and then I 8 2− ) ligands from I 2 and metal-coordinated I 3 − .

AB - The identification of halogen bonded-intermediates is key to understanding the precise mechanism for the generation of I 5 − (and I 8 2− ) ligands from I 2 and metal-coordinated I 3 − . Crystallization of [CuI(CNXyl) 3 ] (1) with I 2 (exhibiting strong halogen bond donor properties), at different molar ratios between the reactants, resulted in a series of (XylNC)Cu I crystal polyiodides formed along with gradual accumulation of iodine, namely [Cu(I 3 )(CNXyl) 3 ] (two crystalline polymorphs 2 I and 2 II ), [Cu(I 3 )(CNXyl) 3 ]·½I 2 (2·½I 2 ) and [Cu(CNXyl) 3 ](I 5 ) (3); all these compounds were studied by X-ray diffractometry. Molecular electrostatic potential (MEP) surface plots were also calculated using density functional theory (DFT) for isolated molecules of 2 and I 2 , showing electrophilic and nucleophilic sites. Halogen bonding in 2·½I 2 was additionally elucidated for both crystal and cluster models, including combined quantum theory of atoms-in-molecules (QTAIM) and one-electron potential (OEP) projections. For model clusters, DFT energetic analysis, quantum theory of atoms-in-molecules, combined with the noncovalent interaction index plot (QTAIM/NCIplot), natural bond orbital (NBO) donor–acceptor charge transfer analysis, and Wiberg bond index (WBI) analysis were used. In the structure of 2·½I 2 , the presence of an I 2 ⋯I 3 − halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I 5 − (and then I 8 2− ) ligands from I 2 and metal-coordinated I 3 − .

UR - https://www.mendeley.com/catalogue/558e7336-c23c-3491-82bd-22c0a26dd068/

U2 - 10.1039/D2QI02634A

DO - 10.1039/D2QI02634A

M3 - Article

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

ER -