2026-10-11T20:38:59Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33950701 2026-09-21T07:08:14Z category_1 category_4 category_21 category_873 category_734 category_931 category_135 portal_63 item_type_3 month_year_09_2026

Catalytic C(sp²)–F Bond Gallylation via Dynamic Ni–Ga Cooperativity Christoph Riesinger (16510958) Mark R. Crimmin (1365135) Biophysics Biochemistry Biotechnology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified Information Systems not elsewhere classified Computational Biology limiting transition state key intermediates identify established mechanistic limitations dynamic heterometallic catalysis computational studies together trimetallic catalytic regimes potentially impeding reactivity catalytic resting state monometallic reactivity catalytic cycle targeted isolation overcome many dynamically switching common need Bimetallic cooperative catalysis has overcome many of the established mechanistic limitations of monometallic reactivity in activating and transforming strong element–element bonds. However, the common need for supporting ligands enforces bimetallic catalyst speciation, potentially impeding reactivity. Here, we report an unsupported Ni–Ga heterometallic system for the conversion of C(sp²)–F into C(sp²)–Ga bonds, capable of dynamically switching between bimetallic and trimetallic catalytic regimes to achieve key steps along the catalytic cycle. Spectroscopic, kinetic, and computational studies together with the targeted isolation of key intermediates identify a bimetallic Ni–Ga bis(olefin) complex as the catalytic resting state and reveal a turnover-limiting transition state for C(sp²)–F activation. This cooperative approach unlocks reactions of electron-rich fluoroarene substrates previously inaccessible to C(sp²)–F bond gallylation in the absence of dynamic heterometallic catalysis. 2026-09-21T00:00:00Z Dataset Dataset 10.1021/jacs.6c16732.s001 https://figshare.com/articles/dataset/Catalytic_C_sp_sup_2_sup_F_Bond_Gallylation_via_Dynamic_Ni_Ga_Cooperativity/33950701 CC BY-NC 4.0