This is an early access version, the complete PDF, HTML, and XML versions will be available soon.
Open AccessArticle
Reactivity of Ammonia in 1,2-Addition to Group 13 Imine Analogues with G13–P–Ga Linkages: The Electronic Role of Group 13 Elements
by
Zheng-Feng Zhang
Zheng-Feng Zhang 1 and
Ming-Der Su
Ming-Der Su 1,2,*
1
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan
2
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 80708, Taiwan
*
Author to whom correspondence should be addressed.
Molecules 2025, 30(15), 3222; https://doi.org/10.3390/molecules30153222 (registering DOI)
Submission received: 3 July 2025
/
Revised: 24 July 2025
/
Accepted: 25 July 2025
/
Published: 31 July 2025
Abstract
Using density functional theory (M06-2X-D3/def2-TZVP), we investigated the 1,2-addition reactions of NH3 with a series of heavy imine analogues, G13=P-Rea (where G13 denotes a Group 13 element; Rea = reactant), featuring a mixed G13–P–Ga backbone. Theoretical analyses revealed that the bonding nature of the G13=P moiety in G13=P-Rea molecules varies with the identity of the Group 13 center. For G13=B, Al, Ga, and In, the bonding is best described as a donor–acceptor (singlet–singlet) interaction, whereas for G13 = Tl, it is characterized by an electron-sharing (triplet–triplet) interaction. According to our theoretical studies, all G13=P-Rea species—except the Tl=P analogue—undergo 1,2-addition with NH3 under favorable energetic conditions. Energy decomposition analysis combined with natural orbitals for chemical valence (EDA–NOCV), along with frontier molecular orbital (FMO) theory, reveals that the primary bonding interaction in these reactions originates from electron donation by the lone pair on the nitrogen atom of NH3 into the vacant p-π* orbital on the G13 center. In contrast, a secondary, weaker interaction involves electron donation from the phosphorus lone pair of the G13=P-Rea species into the empty σ* orbital of the N–H bond in NH3. The calculated activation barriers are primarily governed by the deformation energy of ammonia. Specifically, as the atomic weight of the G13 element increases, the atomic radius and G13–P bond length also increase, requiring a greater distortion of the H2N–H bond to reach the transition state. This leads to a higher geometrical deformation energy of NH3, thereby increasing the activation barrier for the 1,2-addition reaction involving these Lewis base-stabilized, heavy imine-like G13=P-Rea molecules and ammonia.
Share and Cite
MDPI and ACS Style
Zhang, Z.-F.; Su, M.-D.
Reactivity of Ammonia in 1,2-Addition to Group 13 Imine Analogues with G13–P–Ga Linkages: The Electronic Role of Group 13 Elements. Molecules 2025, 30, 3222.
https://doi.org/10.3390/molecules30153222
AMA Style
Zhang Z-F, Su M-D.
Reactivity of Ammonia in 1,2-Addition to Group 13 Imine Analogues with G13–P–Ga Linkages: The Electronic Role of Group 13 Elements. Molecules. 2025; 30(15):3222.
https://doi.org/10.3390/molecules30153222
Chicago/Turabian Style
Zhang, Zheng-Feng, and Ming-Der Su.
2025. "Reactivity of Ammonia in 1,2-Addition to Group 13 Imine Analogues with G13–P–Ga Linkages: The Electronic Role of Group 13 Elements" Molecules 30, no. 15: 3222.
https://doi.org/10.3390/molecules30153222
APA Style
Zhang, Z.-F., & Su, M.-D.
(2025). Reactivity of Ammonia in 1,2-Addition to Group 13 Imine Analogues with G13–P–Ga Linkages: The Electronic Role of Group 13 Elements. Molecules, 30(15), 3222.
https://doi.org/10.3390/molecules30153222
Article Metrics
Article Access Statistics
For more information on the journal statistics, click
here.
Multiple requests from the same IP address are counted as one view.