AbstractThe reactions of [Re(N‐N)(CO)3(PMe3)]OTf (N‐N=2,2′‐bipyridine, bipy; 1,10‐phenanthroline, phen) compounds with tBuLi and with LiHBEt3 have been explored. Addition to the N‐N chelate took place with different site‐selectivity depending on both chelate and nucleophile. Thus, with tBuLi, an unprecedented addition to C5 of bipy, a regiochemistry not accessible for free bipy, was obtained, whereas coordinated phen underwent tBuLi addition to C2 and C4. Remarkably, when LiHBEt3 reacted with [Re(bipy)(CO)3(PMe3)]OTf, hydride addition to the 4 and 6 positions of bipy triggered an intermolecular cyclodimerization of two dearomatized pyridyl rings. In contrast, hydride addition to the phen analog resulted in partial reduction of one pyridine ring. The resulting neutral ReI products showed a varied reactivity with HOTf and with MeOTf to yield cationic complexes. These strategies rendered access to ReI complexes containing bipy‐ and phen‐derived chelates with several C(sp3) centers.