title: Syntheses, X-ray structures, and physicochemical properties of phenoxo-bridged dinuclear nickel(II) complexes: kinetics of transesterification of 2-hydroxypropyl-p-nitrophenylphosphate.
abstract: Four dinuclear nickel(II) complexes [Ni(II)(2)(L(1))(O(2)CMe)(2)(H(2)O)(2)][PF(6)].MeOH.3H(2)O (1), [Ni(II)(2)(L(1))(O(2)CMe)(2)(NCS)] (2), [Ni(II)(2)(L(2))(O(2)CMe)(2)(MeOH)(H(2)O)][ClO(4)] (3), and [Ni(II)(2)(L(2))(O(2)CMe)(2)(MeOH)(H(2)O)][BPh(4)].3MeOH.H(2)O (4) have been synthesized [HL(1): 2,6-bis[N-methyl-N-(2-pyridylethyl)amino]-4-methylphenol; HL(2): 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol]. Complexes 1, 3, and 4 are new while complex 2 was reported previously by Fenton and co-workers (the structure of 2 was presented but no physicochemical properties of this complex were reported; in this work such studies have been completed). X-ray crystallographic analyses of 1 and 4 reveal that each nickel(II) center is six-coordinate, terminally coordinated by two nitrogen donors [(pyridin-2-yl)ethylamine unit in 1 and 3-(pyridin-2-yl)pyrazole moiety in 4], and bridged by an endogenous phenolate ion. Each of the acetate ions in 1 adopts a eta(2)-coordination mode (chelating) whereas in 4 each is coordinated in a mu-eta(1):eta(1) syn-syn bridging mode. In 1 each Ni(II) center has water coordination whereas in 4 one Ni(II) center has a methanol and the other has water coordination. The X-ray structure of 3 could not be determined. The physicochemical properties (electronic spectroscopy and cyclic voltammetry) of the cation of 3 are identical to that of 4. Magnetic susceptibility measurements have revealed the occurrence of ferromagnetic coupling of spins of the nickel(II) centers in 2 [J = +9.80 cm(-1)]. The nickel(II) centers in 1 and 3 are antiferromagnetically coupled, but to different extents [J = -48.4 cm(-1) (1); J = -1.24 cm(-1) (3)]. The magnetic properties are correlated with the nature of bridges between the nickel(II) ions. The two coordinated aqua ligands in 1 and the aqua and methanol ligands in 3 have enabled these dinuclear nickel(II) complexes to function as catalysts in the hydrolysis of 2-hydroxypropyl-p-nitrophenylphosphate (HPNP). Complex 1 is more effective in the conversion of substrate to product (p-nitrophenolate ion) than 3, under identical experimental conditions. Pseudo first-order kinetic treatment has been done for complexes 1 and 3. Temperature-dependent measurements were done to evaluate kinetic/thermodynamic parameters for the hydrolysis/transesterification reaction of HPNP and to propose a mechanistic pathway. The activation parameters are DeltaH(++) = 64 kJ mol(-1), DeltaS(++) = -104 J mol(-1) K(-1) for 1 and DeltaH(++) = 68 kJ mol(-1), DeltaS(++) = -109 J mol(-1) K(-1) for 3. A mechanism consistent with the kinetic data is presented.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, India.
authors.forename: Sukanta
authors.initials: S
authors.lastname: Mandal
authors.forename: V
authors.initials: V
authors.lastname: Balamurugan
authors.forename: Francesc
authors.initials: F
authors.lastname: Lloret
authors.forename: Rabindranath
authors.initials: R
authors.lastname: Mukherjee
mesh_terms: D032701:Biomimetics; D018360:Crystallography, X-Ray; D004951:Esterification; D004952:Esters / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D008280:Magnetics; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010755:Organophosphates; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011199:Potentiometry; D013055:Spectrophotometry, Infrared; D017186:Titrimetry
chemical_list: C436487:2-(hydroxypropyl)-4-nitrophenyl phosphate; D004952:Esters; D009942:Organometallic Compounds; D010755:Organophosphates; D009943:Organophosphorus Compounds; D009532:Nickel