000126582 001__ 126582 000126582 005__ 20240731103324.0 000126582 0247_ $$2doi$$a10.1021/acs.inorgchem.3c00654 000126582 0248_ $$2sideral$$a134084 000126582 037__ $$aART-2023-134084 000126582 041__ $$aeng 000126582 100__ $$aVelasquez, J. D. 000126582 245__ $$aStructure and bonding of halonium compounds 000126582 260__ $$c2023 000126582 5060_ $$aAccess copy available to the general public$$fUnrestricted 000126582 5203_ $$aThe geometrical parameters and the bonding in [D···X···D]+ halonium compounds, where D is a Lewis base with N as the donor atom and X is Cl, Br, or I, have been investigated through a combined structural and computational study. Cambridge Structural Database (CSD) searches have revealed linear and symmetrical [D···X···D]+ frameworks with neutral donors. By means of density functional theory (DFT), molecular electrostatic potential (MEP), and energy decomposition analyses (EDA) calculations, we have studied the effect of various halogen atoms (X) on the [D···X···D]+ framework, the effect of different nitrogen-donor groups (D) attached to an iodonium cation (X = I), and the influence of the electron density alteration on the [D···I···D]+ halonium bond by variation of the R substituents at the N-donor upon the symmetry, strength, and nature of the interaction. The physical origin of the interaction arises from a subtle interplay between electrostatic and orbital contributions (σ-hole bond). Interaction energies as high as 45 kcal/mol suggest that halonium bonds can be exploited for the development of novel halonium transfer agents, in asymmetric halofunctionalization or as building blocks in supramolecular chemistry. 000126582 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/RYC-2017-22853$$9info:eu-repo/grantAgreement/ES/MICINN/CEX2021-001202-M$$9info:eu-repo/grantAgreement/ES/MCINN/PID2019-109119GA-I00$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E07-20R 000126582 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/ 000126582 590__ $$a4.3$$b2023 000126582 592__ $$a0.928$$b2023 000126582 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b8 / 44 = 0.182$$c2023$$dQ1$$eT1 000126582 593__ $$aChemistry (miscellaneous)$$c2023$$dQ1 000126582 593__ $$aPhysical and Theoretical Chemistry$$c2023$$dQ1 000126582 593__ $$aInorganic Chemistry$$c2023$$dQ1 000126582 594__ $$a7.6$$b2023 000126582 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000126582 700__ $$aEcheverría, J.$$uUniversidad de Zaragoza 000126582 700__ $$aÁlvarez, S. 000126582 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000126582 773__ $$g62, 23 (2023), 8980-8992$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669 000126582 8564_ $$s6110703$$uhttps://zaguan.unizar.es/record/126582/files/texto_completo.pdf$$yVersión publicada 000126582 8564_ $$s2827395$$uhttps://zaguan.unizar.es/record/126582/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000126582 909CO $$ooai:zaguan.unizar.es:126582$$particulos$$pdriver 000126582 951__ $$a2024-07-31-09:44:07 000126582 980__ $$aARTICLE