Abstract
A series of monovalent Re complexes, mer-[Re(kappa(3)-2,6-(Ph2PNH)(2)NC5H3)(CO)(3)](+), cis-[Re{kappa(3)-2,6-(Ph2PNMe)(2)NC5H3)(CO)(2)Cl], and mer-[Re(kappa(3)-2,6-(Ph2PNH)(2)NC5H3)(CO)(3)](+). supported by neutral "PN3P" ligands have been synthesized by addition of pincer ligand to Re(CO)(5)X (X = Cl, Br). The products were characterized by multinuclear NMR and single crystal X-ray diffraction studies and showed a dependence on the identity of the halo ligand in starting material and on the substitution pattern of the pincer ligand. The formation of the mer-Re(CO)(3) core geometry and the autoionization of halide ligand in the majority of these species is in marked contrast to the bulk of the literature on the substitution chemistry of Re(I) carbonyl halides. (C) 2017 Elsevier Ltd. All rights reserved.