As part of our recent C-H borylation work we demonstrated that the reaction of NacNacZnH (NacNac = { (2,6-i Pr2C6H3)N(CH3)C}2CH) with an anilinium cation, [(DMT)H] + (DMT = N,N-dimethyl-4-toluidine), to form H2 and [NacNacZn(DMT)] + is exergonic. 14c Initial computational studies indicated that DMT can be displaced from zinc by a heteroarene. The resultant Zn-(heteroaryl-H) complex and free DMT were then calculated to effect C-H zincation with feasible barriers (for solution reactivity). While this FLP-type C-H zincation was calculated to be significantly endergonic, coupling it with a dehydrocoupling step (between NacNacZnH (1) and [(DMT)H] + ) was explored as a route to make the C-H zincation process exergonic overall. Initially, 1 and equimolar 2-methyl-thiophene, 2a (selected as the model substrate given its propensity to undergo C-H borylation using boron-based FLPs), were combined with 10 mol% [(DMT)H][B(C6F5)4]. This led to 41% conversion to the C-H zincation product 3a after heating at 60 °C for 15 h in chlorobenzene (PhCl, Table , entry 1). Under identical conditions in the absence of the ammonium salt no C-H metalation was observed (entry 2). a 1 (0.1 mmol, 1.0 equiv.), 2a (n equiv.), and Brønsted acid (0.01 mmol, 0.1 equiv) in PhCl (0.6 mL). Yield by H NMR spectroscopy versus CH2Br2 added as internal standard at the end. Reaction carried out for 24 h. Reaction carried out at 70 °C.