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Molecules 2017, 22(11), 1955; doi:10.3390/molecules22111955

Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

1
Department of Chemistry, Youngstown State University, Youngstown, OH 44555, USA
2
Instituto de Química Médica (IQM-CSIC), Juan de la Cierva, 3, E-28006 Madrid, Spain
*
Authors to whom correspondence should be addressed.
Received: 17 October 2017 / Revised: 7 November 2017 / Accepted: 9 November 2017 / Published: 12 November 2017
(This article belongs to the Special Issue Halogen Bonds and Beyond)
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Abstract

MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl) for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl) and 1J(C–Cl) provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs. View Full-Text
Keywords: ab initio studies; halogen bonding; structures and binding energies; bonding properties; stretching frequencies; 13C chemical shieldings; EOM-CCSD spin–spin coupling constants ab initio studies; halogen bonding; structures and binding energies; bonding properties; stretching frequencies; 13C chemical shieldings; EOM-CCSD spin–spin coupling constants
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MDPI and ACS Style

Del Bene, J.E.; Alkorta, I.; Elguero, J. Halogen Bonding Involving CO and CS with Carbon as the Electron Donor. Molecules 2017, 22, 1955.

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