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Bond Energies, Bond Lengths and Multiplicity
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Triple-Bonded Boron≡Phosphorus Molecule: Is That Possible?

Jia-Syun Lu1, Ming-Chung Yang1, Ming-Der Su1,2

  • 1Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.

ACS Omega
|August 29, 2019
PubMed
Summary

Sterically bulky substituents stabilize boron-phosphorus triple bonds (R'B≡PR'), making them isolable. Electronic and steric effects of these bulky groups are crucial for the synthetic accessibility of these compounds.

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Area of Science:

  • Computational Chemistry
  • Inorganic Chemistry
  • Quantum Chemistry

Background:

  • The synthesis and isolation of compounds featuring multiple bonds between heavier main group elements remain a significant challenge in chemistry.
  • Previous theoretical studies suggested that boron-phosphorus triple bonds (RB≡PR) are likely fleeting intermediates, difficult to detect experimentally, especially with smaller substituents.

Purpose of the Study:

  • To investigate the effect of substituent variation on the potential energy surfaces of RB≡PR compounds.
  • To identify the conditions and structural features necessary for the experimental isolation of boron-phosphorus triple-bonded species.

Main Methods:

  • Density functional theories (DFT) were employed, including M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp.
  • Theoretical studies focused on analyzing the stability and bonding characteristics of RB≡PR with various substituents (R = H, F, OH, SiH3, CH3, and sterically demanding groups).

Main Results:

  • Theoretical evidence indicates that RB≡PR compounds with small substituents are unstable intermediates.
  • Only RB≡PR molecules with sterically bulky substituents (e.g., Tbt, SiMe(Si*t*Bu3)2, Ar*, Si*i*PrDis2) are significantly stabilized and predicted to be experimentally isolable.
  • The bonding in these stabilized species is best described by a valence-electron bonding model as R'BI PR'.

Conclusions:

  • The experimental accessibility and isolability of triply bonded R'B≡PR' species are critically dependent on the steric bulk of the substituent ligands.
  • Both electronic and steric factors of bulky substituents play a vital role in stabilizing these unusual boron-phosphorus triple bonds.