Employing a neutral "PN3P" pincer to access mer-Re(I) tricarbonyl complexes: Autoionization of a halo ligand and the role of an N-R (R = H, Me) substituent. (15th March 2018)

• Record Type: Journal Article
• Authors: Rao, Gyandshwar Kumar; Korobkov, Ilia; Gabidullin, Bulat; Richeson, Darrin
• Is Part Of: Polyhedron. Volume 143(2018)
• Page Start: 62
• Page End: 69
• Publication Date: 2018-03-15
• Subjects: Rhenium -- Pincer -- Meridional -- PNP -- Autoionization; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2017.08.020
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Monovalent Re complexes, mer- [Re{κ 3 -2, 6-(Ph2 PNH)2 NC5 H3 }(CO)3 ] +, cis -[Re{κ 3 -2, 6-(Ph2 PNMe)2 NC5 H3 }(CO)2 Cl], and mer- [Re{κ 3 -2, 6-(Ph2 PNMe)2 NC5 H3 }(CO)3 ] + were prepared by addition of pincer ligand to Re(CO)5 X (X = Cl, Br). The products showed a dependence on the Re-X group and the ligand NR substituent. The formation of the mer -Re(κ 3 -2, 6-{Ph2 PNR}2 NC5 H3 }(CO)3 + cations contrasts with the reported Re(I) substitution chemistry. Abstract: A series of monovalent Re complexes, mer- [Re{κ 3 -2, 6-(Ph2 PNH)2 NC5 H3 }(CO)3 ] +, cis -[Re{κ 3 -2, 6-(Ph2 PNMe)2 NC5 H3 }(CO)2 Cl], and mer- [Re{κ 3 -2, 6-(Ph2 PNMe)2 NC5 H3 }(CO)3 ] + supported by neutral "PN3 P" 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.