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Be(CO)3 as a Nontraditional Lewis Base Engaging in Halogen Bonding.

Zhaohui Jia1, Qingzhong Li1, Steve Scheiner2

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Beryllium tricarbonyl (Be(CO)3) forms halogen bonds with halogenated molecules. These bonds range from noncovalent to partially covalent, influenced by the halogen and molecular structure.

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Area of Science:

  • Inorganic Chemistry
  • Computational Chemistry
  • Supramolecular Chemistry

Background:

  • The highest occupied molecular orbital (HOMO) of beryllium tricarbonyl (Be(CO)3) exhibits lone pair characteristics.
  • This lone pair can act as an electron donor in the formation of halogen bonds.

Purpose of the Study:

  • To investigate the nature and strength of halogen bonds formed between Be(CO)3 and various halogenated compounds.
  • To explore the influence of molecular structure and halogen type on halogen bond characteristics.

Main Methods:

  • Quantum chemical calculations were employed to model interactions.
  • Be(CO)3 was paired with halogenated molecules: XF, XCl, XCN, and XCF3 (where X = I, Br, Cl).

Main Results:

  • Noncovalent halogen bonds formed with XCN and XCF3 (2.2–9.7 kcal/mol), showing increased strength with larger halogens.
  • Stronger interactions (≥40 kcal/mol) with XF and XCl exhibited covalent character, termed halogen sharing.
  • Halogen sharing resulted in X-C bond stretching and red-shifted vibrational frequencies.

Conclusions:

  • Be(CO)3 can participate in both noncovalent and partially covalent halogen bonds.
  • The strength and nature of the interaction are dependent on the halogenated partner, with XF and XCl forming stronger, more covalent bonds.
  • Trends in interaction strength differ between noncovalent and halogen-shared complexes.