화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.121, No.40, 7717-7725, 2017
Real-Space Bonding Indicator Analysis of the Donor Acceptor Complexes X3BNY3, X(3)AINY(3), X3BPY3, and X(3)AIPY(3) (X, Y = H, Me, CI)
Calculations of real-space bonding indicators (RSBI) derived from Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D), Non-Covalent Interactions index (NCI), and Density Overlap Regions Indicator (DORI) toolkits for a set of 36 donor acceptor complexes X3BNY3 (1, la lh), X3AlNY3 (2, 2a-2h), X3BPY3 (3, 3a-3h), and X(3)AIPY(3) (4, 4a-4h) reveal that the donor acceptor bonds comprise covalent and ionic interactions in varying extents (X = Y = H for 1-4; X = H, Y = Me for la-4a; X = H, Y = Cl for lb-4b; X = Me, Y = H for lc-4c; X, Y = Me for ld-4d; X = Me, Y = Cl for le-4e; X = Cl, Y = H for if--4f; X = Cl, Y = Me for lg-4g; X, Y = Cl for lh-4h). The phosphinoboranes X3BPY3 (3, 3a-3h) in general and Cl(3)BPMe3 (3f) in particular show the largest covalent contributions and the least ionic contributions. The aminoalanes X3AlNY3 (2, 2a-2h) in general and Me3AlNCl3 (2e) in particular show the least covalent contributions and the largest ionic contributions. The aminoboranes X3BNY3 la lh) and the phosphinoalanes X3AlPY3 (4, 4a-4h) are midway between phosphinoboranes and aminoalanes. The degree of covalency and ionicity correlates with the electronegativity difference BP (DEN = 0.15) < AlP (DEN = 0.58) < BN (DEN = 1.00) < AIN (DEN = 1.43) and a previously published energy decomposition analysis (EDA). To illustrate the importance of both contributions in Lewis formula representations, two resonance formulas should be given for all compounds, namely, the canonical form with 'formal charges denoting covalency and the arrow notation pointing from the donor to the acceptor atom 'to emphasis ionicity. If the Lewis formula mainly serves to show the atomic connectivity, the most significant should-be shown. Thus, it is legitimate to present aminoalanes using arrows; however, for phosphinoboranes the canonical form with formal charges is more appropriate.