In contrast to the systems containing [BAr F ] -anions, reactions between NacNacZnH and [(DMT)H][OTf] afforded crystals of the dimeric complex {NacNacZn(-OTf)}2, 14 (Figure ). In this structure each OTf anion is bound to two zinc centers forming an eight-membered ring reminiscent of dimeric NacNacZn(carboxylate) derivatives. In-situ NMR studies also revealed that DMT does not displace [OTf] -from zinc in 14 in solution (Fig. ). This suggests the poor outcomes using [OTf] -in the catalytic C-H zincation is due to the more coordinating nature of the [OTf] -anion toward zinc (relative to the [BAr F ] -anions) which presumably blocks the heteroarene from interacting with the zinc center.