Gas-Phase Reactivity of AuSiO3– Anion Clusters with n-Alkanes (C1–C4): Distinguishing Capture, Stabilized Association, and C–H Bond Activation
- 1Rocket Force University of Engineering , ,
- 2National Key Laboratory of Solid Rocket Propulsion , ,
Abstract
The reactivity of heteronuclear gold-silicon oxide cluster anion AuSiO3– toward small alkanes (C1–C4) has been experimentally investigated at room temperature by employing a homemade reflectron time-of-flight mass spectrometer. Experimental results reveal distinct reaction channels for these systems, which produce hydrogen-containing dissociation products (SiO3H–) and associative adducts (AuSiO3CnH2n+2–, n = 1–4). While the total depletion (capture) rate increases with increasing chain length, the branching ratio of dissociation products correspondingly decreases. Density functional theory calculations demonstrate that the two-fold-coordinated gold ion (Au+) anchored on the AuSiO3– cluster proceeds via an oxidative addition mechanism involving homolytic bond cleavage. Both RRKM calculations and MESMER master-equation simulations reveal that for larger alkanes such as C4H10, the rapidly growing density of vibrational states with increasing chain length shifts the competition from product dissociation toward collisional stabilization, thereby favoring associative adduct formation over dissociation pathways─a stark contrast to the behavior observed in the AuSiO3––CH4 reaction. This work provides novel insights into the competition among collisional capture, stabilized association, and C–H bond activation in small-molecule alkanes.
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BibTeX
@article{chen2026gasphase,
title = {{Gas-Phase Reactivity of AuSiO3– Anion Clusters with n-Alkanes (C1–C4): Distinguishing Capture, Stabilized Association, and C–H Bond Activation}},
author = {Yiming Chen and Guofeng Jin and Yutian Li and Yingying Wang and Zhipan Ma and Xueqi Zhao and Zhanrong Zhou},
journal = {ACS Omega},
year = {2026},
month = nov,
doi = {10.1021/acsomega.6c09519},
url = {https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c09519/5462187/Gas-Phase-Reactivity-of-AuSiO3-Anion-Clusters-with},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Gas-Phase Reactivity of AuSiO3– Anion Clusters with n-Alkanes (C1–C4): Distinguishing Capture, Stabilized Association, and C–H Bond Activation
AU - Yiming Chen
AU - Guofeng Jin
AU - Yutian Li
AU - Yingying Wang
AU - Zhipan Ma
AU - Xueqi Zhao
AU - Zhanrong Zhou
PY - 2026
DA - 2026/11/02
JO - ACS Omega
DO - 10.1021/acsomega.6c09519
UR - https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c09519/5462187/Gas-Phase-Reactivity-of-AuSiO3-Anion-Clusters-with
AB - The reactivity of heteronuclear gold-silicon oxide cluster anion AuSiO3– toward small alkanes (C1–C4) has been experimentally investigated at room temperature by employing a homemade reflectron time-of-flight mass spectrometer. Experimental results reveal distinct reaction channels for these systems, which produce hydrogen-containing dissociation products (SiO3H–) and associative adducts (AuSiO3CnH2n+2–, n = 1–4). While the total depletion (capture) rate increases with increasing chain length, the branching ratio of dissociation products correspondingly decreases. Density functional theory calculations demonstrate that the two-fold-coordinated gold ion (Au+) anchored on the AuSiO3– cluster proceeds via an oxidative addition mechanism involving homolytic bond cleavage. Both RRKM calculations and MESMER master-equation simulations reveal that for larger alkanes such as C4H10, the rapidly growing density of vibrational states with increasing chain length shifts the competition from product dissociation toward collisional stabilization, thereby favoring associative adduct formation over dissociation pathways─a stark contrast to the behavior observed in the AuSiO3––CH4 reaction. This work provides novel insights into the competition among collisional capture, stabilized association, and C–H bond activation in small-molecule alkanes.
SN - 2470-1343
ER -