title: Ligand substituents effect on 10Dq.
abstract: Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Ni(ClO(4))(2)·6H(2)O in methanol in 3:1M proportion at room temperature yields [NiL(3)](ClO(4))(2)·2H(2)O. The X-ray crystal structure of the cation NiL(3)(2+) has been determined. Aminolysis of the three epoxide rings in NiL(3)(2+) by 4-substituted anilines in boiling water without any Lewis acid catalyst gives a family of Ni(II) complexes with octahedral NiL(6)(2+) core. In these complexes, crystal field splitting 10Dq varies from 11601 to 15798 cm(-1) in acetonitrile. The variation in 10Dq is found to be satisfactorily linear (r(2)=0.951) with the Hammett σ(R) parameter of the substituent on the anilino fragment. 10Dq increases with the increase in the electron donation ability of the substituent.
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Calcutta 700 032, India.
authors.forename: Nirmal K
authors.initials: NK
authors.lastname: Shee
authors.forename: Michael G B
authors.initials: MG
authors.lastname: Drew
authors.forename: Dipankar
authors.initials: D
authors.lastname: Datta
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D004583:Electrons; D004852:Epoxy Compounds / Q000737:chemistry; D008024:Ligands; D010618:Phenanthrolines / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D000097:Acetonitriles; D004852:Epoxy Compounds; D008024:Ligands; D010618:Phenanthrolines; C025205:1,10-phenanthroline; C032159:acetonitrile