title: New [LNiII2]+ complexes incorporating 2-formyl or 2,6-diformyl-4-methyl phenol as inhibitors of the hydrolysis of the ligand L3-: Ni...Ni ferromagnetic coupling and S=2 ground states.
abstract: Reaction of the dinucleating ligand H3L (2-(2'-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) with Ni(NO3)(2).6H2O produces the dimer of monomers [Ni(HL1)]2(NO3)(2).4H2O (1.4H2O) following the hydrolysis of H3L. If the reaction occurs in the presence of 2-formylphenol (Hfp) or 2,6-diformyl-4-methylphenol (Hdfp), this hydrolysis is prevented by incorporation of these co-ligands into the structure and stabilization of the new complexes [Ni2L(fp)(H2O)].3H2O (2.3H2O) and [Ni2L(dfp)].4.5H2O (3.4.5H2O), respectively. Complexes 2 and 3 may be considered to be structural models of the active site of urease, where coordination of the carbonyl ligand mimics binding of urea. In complex 2, coordination of terminal water reproduces the binding of this substrate of the enzyme to the active site. In both dinuclear complexes, the NiII ions are coupled ferromagnetically to yield S=2 ground states, whereas complex 1 exhibits weak intradimer antiferromagnetic exchange through hydrogen bonds. The magnetic data can be modeled by using the Van Vleck equation, incorporating intermolecular interactions, or by diagonalization of a spin Hamiltonian that includes single-ion anisotropy.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India.
authors.forename: Alok Ranjan
authors.initials: AR
authors.lastname: Paital
authors.forename: Wing Tak
authors.initials: WT
authors.lastname: Wong
authors.forename: Guillem
authors.initials: G
authors.lastname: Aromí
authors.forename: Debashis
authors.initials: D
authors.lastname: Ray
mesh_terms: D003408:Cresols / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006868:Hydrolysis; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: C474508:2,6-diformyl-4-methylphenol; D003408:Cresols; D008024:Ligands; D009942:Organometallic Compounds; D013455:Sulfur; D009532:Nickel