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Borylene as an electron-pair donor for PB pnicogen bonds

Abstract

Ab initio MP2/aug’-cc-pVTZ calculations have been performed on the complexes (CO)2(HB):PXH2 and (N2)2(HB):PXH2, for X = F, Cl, NC, OH, CN, CCH, CH3, and H, in order to investigate the properties of these complexes which are stabilized by PB pnicogen bonds, with B the electron-pair donor. The binding energies of these complexes exhibit an exponential dependence on the P-B distance, but they do not correlate with the MEP minima for (CO)2(HB) and (N2)2(HB), nor with the MEP maxima for PXH2. For fixed X, the binding energy of (N2)2(HB):PXH2 is greater than that of (CO)2(HB):PXH2. Charge-transfer stabilizes both series of complexes, and occurs from the B electron pair to the antibonding P-A σ orbital, with A the atom of X directly bonded to P. These charge-transfer energies also exhibit an exponential dependence on the P-B distance. In the complexes (CO)2(HB):PXH2, there is a second charge-transfer interaction from the lone pair on P to the antibonding π orbitals of the two C-O groups. Electron density analyses indicate that the PB bonds in these complexes are stabilized by relatively weak interactions with little covalent character. The chemical shieldings of 11B are essentially unaffected by complex formation. In contrast, the shieldings of 31P increase from 10 to 50 ppm in the four most strongly bound complexes, but decrease by −4 to −12 ppm in the remaining complexes. For each series of complexes, EOM-CCSD spin-spin coupling constants 1pJ(P-B) increase quadratically with decreasing P-B distance. For fixed X, 1pJ(P-B) is greater for (CO)2(HB):PXH2 compared to (N2)2(HB):PXH2.

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Acknowledgments

This work was carried out with financial support from the Ministerio de Economía y Competitividad (Project No. CTQ2015-63997-C2-2-P) and Comunidad Autónoma de Madrid (S2013/MIT2841, Fotocarbon). Thanks are also given to the Ohio Supercomputer Center and CTI (CSIC) for their continued computational support.

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Correspondence to Ibon Alkorta.

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This paper is dedicated to Professor Lou Massa on the occasion of his Festschrift: A Path through Quantum Crystallography.

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Alkorta, I., Elguero, J. & Del Bene, J.E. Borylene as an electron-pair donor for PB pnicogen bonds. Struct Chem 28, 1419–1427 (2017). https://doi.org/10.1007/s11224-017-0912-4

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Keywords

  • Borylene
  • Boranylidene
  • PB pnicogen bonds
  • Structures and binding energies
  • Charge-transfer interactions
  • Chemical shieldings
  • EOM-CCSD spin-spin coupling constants