Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide We computationally explored the influence of two Lewis bases ( N -heterocyclic carbene (NHC) and trimethylphosphine (PMe 3 ) and four metal cations (Li +, Na +, K +, and Mg 2+ ) used in experiments on the isomerizations of disilyne Si 2 Ph 2 (Ph = C 6 H 5 ) and Si 2 Tip 2 (Tip = 2,4,6- i Pr 3 C 6 H 2 ) in this work. Computations demonstrated that kinetically, both NHC and PMe 3 increase the energy barriers and thus stabilize disilavinylidene. Thermodynamically, however, NHC can reduce the energy gap between disilyne and disilavinylidene, while PMe 3 stabilizes disilavinylidene or slightly influences the relative stability. Further analyses showed that it is polarization that governs the energy barriers and gaps. When metal cations are further introduced, they tend to adopt the end-on bonding mode and cooperate with Lewis bases via a push–pull effect. The electrostatic interaction between Mg 2+ and NHC-stabilized disilyne can even improve the relative stability of disilyne. Therefore, the synergy between NHC and Mg 2+ can help the preparation of disilyne if the energy barrier from Lewis base-stabilized disilavinylidene to disilyne is overcome, but to obtain disilavinylidene, it might be better to use phosphine alone without metal cations.
Source: Organometallics
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4402265957