Novel Bonding Mode in Phosphine Haloboranes

Abstract

We have predicted, using a wide range of theoretical models, the potential energy surfaces of dative bond stretching in some phosphine haloboranes and closely associated analogues. It is shown that these dative complexes demonstrate unusual bond stretching potentials that are characterized by having multiple inflection points and are not able to be fit to any traditional Morse or Lennard-Jones-type curve. Specifically, in the case of Cl 3 B–PH 3 , this effect is so pronounced that the surface actually exhibits two distinct minima. To the best of our knowledge, this is the first example of such a unique bonding phenomenon reported for these species and is explained by the competition between the energetic cost of the required pyramidalization of the Lewis acid to form a dative bond and the stabilization from the favorable attraction between the Lewis acid and base. When the cost of pyramidalization of the Lewis acid is high relative to the strength of the interaction between the acid and base, the potential well associated with dative bonding is significantly weakened and the result is a relatively flat potential energy surface that is susceptible to the unusual characteristics described herein.

Clustering of H2SO4 with BX3 (X = H, F, Cl, Br, CN, OH) compounds creates strong acids and superacids

“…Boron compounds are of interest because of their unique properties as Lewis acids [1][2][3][4], hydrogen storage compounds [5][6][7][8], and as catalysts in chemical reactions [9,10]. Also, because of the electron deficiency of the B atom, boron compounds are used as strong anion receptors [11,12].…”

Stability and Electronic Structure of Donor–Acceptor Stabilized Group 13/15 Oligomers

“…Pyramidalization of boron centers in [H 2 BEH 2 ] 10 and BH 3 prior to the DA bond formation is endothermic, but it lowers LUMO energy levels, which facilitates DA bond formation. Almas et al noted that upon formation of DA bonds in the R 3 BPH 3 , the electrostatic interaction between fragments plays a larger role than pyramidalization of the boron center. A less energetically demanding pyramidalization of larger Al or Ga centers is accompanied by a more electrostatic nature of the interaction with the LB, which increases DA bond energy.…”

“…IP and EA computed at the MP2/aug-cc-DZVP//B3LYP/def2-TZVP level of theory for different oligomers show trends similar to energies of HF and KS frontier orbitals (Figure 5). 43 noted that upon formation of DA bonds in the R 3 BPH 3 , the electrostatic interaction between fragments plays a larger role than pyramidalization of the boron center. A less energetically demanding pyramidalization of larger Al or Ga centers is accompanied by a more electrostatic nature of the interaction with the LB, which increases DA bond energy.…”

Isosterism in pyrrole via azaboroles substitution, a theoretical investigation for electronic structural, stability and aromaticity

“…Inorganic materials, such as B–O and N–B compounds, have great oxidation resistance, high thermodynamic stability and are more rigid at high temperatures [ [14] , [15] , [16] ]. The resonance stabilization in a variety of systems, including boron-nitrogen coronenes, borazenes, phosphazenes, and boron-phosphorous nanographene-like material, has been linked to this high stability [ 13 , 17 , 18 ].…”