Nucleophilic additions to coordinated 1,10-phenanthroline: intramolecular, intermolecular, reversible, and irreversible

KN(SiMe3)2 reacts with [Re(CO)3(phen)(PMe3)]OTf via reversible addition to the phen ligand and irreversible deprotonation of the PMe3 ligand followed by intramolecular attack to phen by the deprotonated phosphane, whereas MeLi irreversibly adds to phen. The addition of MeLi has been shown to be intermolecular, unlike previously known nucleophilic additions to pyridines.The authors thank MINECO and FEDER (grant CTQ2015-70231-P) and Principado de Asturias (grantFC-15-GRUPIN14-103) forfunding, and Ministerio de Educación for an FPU predoctoral fellowship (to R.A.).Peer reviewe