title: Synthesis, structure, and spectroscopic properties of chiral oxorhenium(V) complexes incorporating polydentate ligands derived from L-amino acids: a density functional theory/time-dependent density functional theory investigation.
abstract: The oxorhenium(V) complexes [Re (V)O(L A)Cl 2] bearing the (N-2-pyridylmethyl) of l-valine (HL A (1)), l-leucine (HL A (2)), and l-phenylalanine (HL A (3)) and [Re (V)O(L B)Cl] containing the {(N-2pyridylmethyl)-(N-(5-nitro-2-hydroxybenzyl)} of l-valine (H 2L B (1)), l-leucine (H 2L B (2)), and l-phenylalanine (H 2L B (3)) are presented in this article. The complexes are isolated in enantiomeric pure form examined from X-ray structure determination. The complexes are characterized by spectroscopic and electrochemical methods. The molecular structures observed in the solid state are grossly preserved in solution ( (1)H, (13)C, and circular dichroism spectra). Gas-phase geometry optimization and the electronic structures of [Re (V)O(L A (1))Cl 2], [Re (V)O(L A (2))Cl 2], and [Re (V)O(L B (2))Cl] have been investigated with the framework of density functional theory. The absorption and circular dichroism spectra of the complexes were also calculated applying time-dependent density functional theory (TDDFT) using the conductor-like polarizable continuum solvent model to understand the origin of the electronic excitations. The chemical shift ( (1)H and (13)C) as well as (1)H- (1)H spin-spin coupling constant were also computed by the gauge-independent atomic orbital method, and the computed values are consistent with the experimental data.
authors: Inorganic Chemistry Section, Department of Chemistry, Jadavpur University, Kolkata, 700 032, India.
authors: Sucharita
authors: S
authors: Basak
authors: Kajal Krishna
authors: KK
authors: Rajak
mesh_terms: D000042:Absorption; D000596:Amino Acids / Q000737:chemistry*; D002942:Circular Dichroism; D004563:Electrochemistry; D004583:Electrons; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D055095:Optics and Photonics; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D012211:Rhenium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013997:Time Factors
chemical_list: D000596:Amino Acids; D008024:Ligands; D009942:Organometallic Compounds; C015428:perrhenate; D012211:Rhenium