Next Article in Journal
Lithium-Decorated C26 Fullerene in DFT Investigation: Tuning Electronic Structures for Enhanced Hydrogen Storage
Previous Article in Journal
Essential Per- and Polyfluoroalkyl Substances (PFAS) in Our Society of the Future
Previous Article in Special Issue
Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
This is an early access version, the complete PDF, HTML, and XML versions will be available soon.
Article

Reactivity of Ammonia in 1,2-Addition to Group 13 Imine Analogues with G13–P–Ga Linkages: The Electronic Role of Group 13 Elements

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
(This article belongs to the Special Issue Exclusive Feature Papers in Inorganic Chemistry, 3rd Edition)

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.
Keywords: Imine Analogues; Group 13 Elements; Ammonia; 1,2-Addition Reactions Imine Analogues; Group 13 Elements; Ammonia; 1,2-Addition Reactions

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

Back to TopTop