A strategy for affecting ortho-versus meta/para selectivity in Ir-catalyzed C-H borylations (CHBs) of phenols is described. From selectivity observations with ArylOBpin (pin-7 pinacolate), it is hypothesized that an electrostatic interaction between the partial negatively,charged OBpin group and the partial positively charged bipyridine ligand of the catalyst favors ortho selectivity. Experimental and computational studies designed to test this hypothesis support it. From further computational work a second generation, in silico designed catalyst emerged; where replacing Bpin with Beg (eg, = ethylene glycolate) was predicted to significantly improve ortho selectivity. Experinientally, reactions employing B(2)eg(2) gave ortho selectivities > 99%. Adding triethylamine significantly improved conversions. This ligand-substrate electrostatic interaction provides a unique control element for selective C-H functionalization.