Catalytic Hydrolysis Of P-nitrophenyl Picolinate Research Articles

Remarkable reactivity of alkoxide/acetato-bridged binuclear copper(II) complex as artificial carboxylesterase.

Bromo-containing binuclear Schiff base copper(II) complex, Cu2L(OAc), with an alkoxo/acetato-bridged moiety was employed as a model of carboxylesterases to promote the hydrolytic cleavage of p-nitrophenyl picolinate (PNPP). Furthermore, the reactivity of a mononuclear complex (CuHL) was evaluated for comparing it with that of binuclear one. The results reveal that the as-prepared binuclear Cu2L(OAc) efficiently accelerated the hydrolysis of PNPP, giving rise to excess four orders of magnitude rate enhancement in contrast to the un-catalyzed reaction. Cu2L(OAc) represented an enzyme-like bell-shaped pH-responsive kinetic behavior. Moreover, the binuclear one is more reactive than its mononuclear analogue (CuHL) by two orders of magnitude. The total efficiency of Cu2L(OAc) is about 61-fold than that of its mononuclear analogue, CuHL. In addition, a contrast experiment reveals that binuclear Cu2L(OAc) displayed good activity in the hydrolysis of PNPP as well another active ester, i.e., S-2-benzothiazolyl 2-amino-alpha-(methoxyimino)-4-thiazolethiolacetate (AE-active ester). Noteworthyly, it was found that mononuclear one inspired more obvious rate enhancement in the hydrolysis of AE-active ester relative to PNPP hydrolysis. The estimated pK a1 of bound water on the binuclear Cu2L(OAc) using second derivative method (SDM) is relatively smaller than that for CuHL by a gap of about 0.8 pK unit, which facilitates the hydrolysis of PNPP. Four orders of magnitude rate enhancement was observed for the catalytic hydrolysis of p-nitrophenyl picolinate (PNPP) by one μ-alkoxide/acetato-bridged binuclear copper(II) complex under physiological conditions. Substrate specificity of the resulting binuclear complexes was observed for the hydrolysis of PNPP and AE-active ester.

Studies on Schiff Base Complexes with Aza-Crown Ether Pendants as Synthetic Hydrolases for p-Nitrophenyl Picolinate in Brij35 Surfactant Micellar Solution

Schiff base complexes with aza-crown ether pendants have been synthesized and employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP) in Brij35 surfactant micellar solution. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have also been examined. The rate increases with pH of the buffered Brij35 micellar solution under 25°C; all four complexes exhibited high activity in the catalytic PNPP hydrolysis. The catalytic activity of the phenyl-bridged Schiff base complex is larger than that of ethyl-bridged Schiff base complex for the same substituent and metal. The catalytic activity of manganese(III) complex is superior over cobalt(II) complex in catalyzing hydrolysis of PNPP under the same ligand. The pseudo-first-order rate for PNPP hydrolysis catalyzed by CoL1 containing aza-crown ether is 2.96 × 104 times that of spontaneous hydrolysis of PNPP in Brij35 surfactant micellar solution at pH = 7.60, [S] = 2.0 × 10−4 mol dm−3.

Hydrolytic activity of μ-alkoxide/acetato-bridged binuclear Cu(II) complexes towards carboxylic acid ester

Two μ-alkoxide/acetate-bridged small molecule binuclear copper(II) complexes were synthesized, and used to promote the hydrolysis of a classic carboxylic acid ester, p-nitrophenyl picolinate (PNPP). Both binuclear complexes exhibited good hydrolytic reactivity, giving rise to ca. 15547- and 17462-fold acceleration over background value for PNPP hydrolysis at neutral conditions, respectively. For comparing, activities of the other two mononuclear analogues were evaluated, revealing that binuclear complexes show approximately 150- and 171-fold kinetic advantage over their mononuclear analogues. This study reports the hydrolysis of p-nitrophenyl picolinate (PNPP) with increase of rate acceleration up to four orders of magnitude by two μ-alkoxide/acetato-bridged binuclear copper(II) complexes when compared to uncatalysed reaction. Furthermore, the two binuclear complexes were more active than their mononuclear analogues in the catalytic hydrolysis of PNPP.

Mono-Schiff base complexes with aza-crown ether or morpholino pendants as synthetic hydrolases for p-nitrophenyl picolinate cleavage

Mono-Schiff base complexes of Co(II) and Mn(III) with either benzo-10-aza-crown ether pendants (MnL 2 1 Cl, MnL 2 2 Cl) or morpholino pendants (MnL 2 3 Cl, CoL 2 3 ) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP). A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have also been examined. The rate increases with pH of the buffer solution; all four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogs MnL 2 3 Cl and CoL 2 3 , the crowned Schiff base complexes (MnL 2 1 Cl, MnL 2 2 Cl) exhibited higher catalytic activity. The pseudo-first-order rate constant for the PNPP hydrolysis catalyzed by the complex MnL 2 1 Cl, containing a benzo-10-aza-crown ether pendant, is 1.84 × 103-fold higher than that of spontaneous hydrolysis of PNPP at pH 7.60, 25 °C, [S] = 2.0 × 10−4 mol dm−3. Four mono-Schiff base complexes of Mn(III) and Co(II) with either benzo-10-aza-crown ether pendants (MnL 2 1 Cl, MnL 2 2 Cl) or morpholino pendants (MnL 2 3 Cl, CoL 2 3 ) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP). The effects of ligand structure and reaction temperature on PNPP catalytic hydrolysis have been also discussed. All four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogy MnL 2 3 Cl and CoL 2 3 , the crowned Schiff base complexes MnL 2 1 Cl and MnL 2 2 Cl exhibit higher catalytic activity, the catalytic activity of the complexes follows the order Mn(III) > Co(II) under the same ligand.

Metallovesicular catalytic hydrolysis of p-nitrophenyl picolinate catalyzed by zinc(II) complexes of pyridyl ligands in vesicular solution

The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by the Zn(II) complexes of 6-(n-butyloxymethyl)-2-(hydroxymethyl)pyridine and 6-(n-dodecyloxymethyl)-2-(hydroxymethyl)pyridine was kinetically investigated by observation of the rates of release of p-nitrophenol in a vesicular solution at different pH values and temperatures. A 1:1 ligand:Zn 2+ stoichiometry was found to produce the most active species based on a kinetic version of the Job plot analysis. Experimental results also showed that the complex formed from ligand 2 and Zn 2+ exhibited a more remarkable rate acceleration effect on the hydrolysis of PNPP in vesicular solution than that formed from ligand 1 and Zn 2+.

Catalytic Hydrolysis of P-Nitrophenyl Picolinate by Triethanolamine Co(II) Complex-Based Metallomicelle

The catalytic hydrolysis of p-nitrophenyl picolinate (PNPP) by triethanolamine Co(II) complex in the presence or in the absence of CTAB and Triton X-100 micelle was investigated. The results indicated that triethanolamine Co(II) complex promoted the hydrolysis of PNPP by the addition of the catalytic effect of triethanolamine and Co(II), however, in the presence of CTAB and Triton X-100 micelle, triethanolamine Co(II) complex exhibited a remarkably catalytic effect on the hydrolysis of PNPP, indicating the formation of the metallomicelle. According to the proposed ternary complex kinetic model for metallomicellar catalysis, the obtained thermodynamic and kinetic parameters explained well the mechanism of the catalytic hydrolysis of PNPP.

Catalytic Hydrolysis of p-Nitrophenyl Picolinate by Triethanolamine [Co(II)] Complex-Based Metallomicelle

The catalytic hydrolysis of p-nitrophenyl picolinate (PNPP) by triethanolamine Co(II) complex in the presence or in the absence of CTAB and Triton X-100 micelle was investigated. The results indicated that triethanolamine Co(II) complex promoted the hydrolysis of PNPP by the addition of the catalytic effect of triethanolamine and Co(II), however, in the presence of CTAB and Triton X-100 micelle, triethanolamine Co(II) complex exhibited markably catalytic effect on the hydrolysis of PNPP, indicating the formation of the metallomicelle. According to the proposed ternary complex kinetic model for metallomicellar catalysis, the obtained thermodynamic and kinetic parameters explained well the mechanism of the catalytic hydrolysis of PNPP.

Hydrolysis Kinetics of p-Nitrophenyl Picolinate Catalyzed by Mono-Schiff Base Complexes with Aza-Crown Ether or Morpholino Pendants in CTAB Surfactant Micellar Solution

Two mono-Schiff base manganese (III) and cobalt (II) complexes with benzo-10-aza-crown ether pendants (), and the analogy with morpholino pendants () have been synthesized and employed as models for hydrolase enzymes to promote the hydrolysis of p-nitrophenyl picolinate (PNPP) in the buffered CTAB micellar solution. The kinetic mathematical model and mechanism cleavage on PNPP hydrolysis catalyzed by these complexes was proposed. The effects of complexes structure and reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the reactive rate increases with pH of the buffered CTAB micellar solution; all four complexes exhibited high activity for the catalytic PNPP hydrolysis in the buffered CTAB micellar solution. In comparison with the crown-free analogy and , the crowned Schiff base complexes and exhibit higher catalytic activity for promoting PNPP hydrolysis.

Metallomicellar Catalysis: Hydrolysis of PNPP Catalyzed by Copper(II), Zinc(II), Cerium(IV) Complexes with Long Alkyl Pyridine Ligands in CTAB Micellar Solution

A kind of new functional surfactant with substituted long alkyl pyridine was synthesized and its Ce(IV), Zn(II), and Cu(II) complexes were used as hydrolytic metalloenzyme models. The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by the metallomicelles in CTAB micellar solution was investigated at different pH and 30°C. Kinetic parameters of catalytic hydrolysis were obtained by employing the ternary complex kinetic model for metallomicellar catalysis. Effects of the structure of ligands and microenvironment of reaction on the hydrolytic reaction of PNPP have been discussed in detail. From the apparent rate constants (k obsd ) of the catalytic hydrolysis of PNPP, it can be seen that the catalytic effect of complexes of ligand L2 with long hydrocarbon chain was stronger than that of ligand L1, and complex CuL2 showed higher catalytic efficacy on the hydrolytic reaction than those of ZnL2 and CeL2. However, experiment results in this article showed that ZnL2 and CeL2 are more susceptible to environment than CuL2. The catalytic mechanism was proposed, and the possibly active species for the catalytic hydrolysis of PNPP was determined to be the hydroxylated metal complex.

Kinetic Study on P-Nitrophenyl Picolinate Hydrolysis Promoted by the Complex Bis(O,O'-Di(2-Benzyl)Dithiophosphato)Nickel(Ii)

The complex Ni[S2P(OCH2Ph)2]2 (MR) was synthesised and characterised by elemental analysis, IR spectroscopy and 1H NMR spectroscopy. The hydrolysis of p-nitrophenyl picolinate (PNPP) as promoted by this complex was investigated by the UV-vis method, the results showing that MR acts as a very efficient catalyst. The specific absorption spectra of the hydrolytic reaction systems indicated that the key intermediate, made up of PNPP and MR was formed during reaction. Based on these spectra, a mechanism for the catalytic hydrolysis of PNPP has been proposed and a kinetic mathematical model established.

Synthesis and Studies of Hydrolysis of p-nitrophenyl picolinate catalysed by Schiff base zinc (II) complexes with aza-crown ether or morpholino-pendants

Four Schiff base zinc (II) complexes with either benzo-10-aza-crown ether pendants or morpholino-pendants have been synthesised and employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP). A kinetic model of PNPP cleavage catalysed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have been also examined. The rate increases with pH of the buffer solution; all four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with their crown-free analogues, the crowned Schiff base complexes exhibit higher catalytic activity. The catalytic activity of a phenyl-bridged Schiff base complex is larger than that of an ethyl-bridged Schiff base complex under the same substitute groups and metal ion.

Studies on p-Nitrophenyl Picolinate (PNPP) Cleavage by Mono-Schiff Base Complexes with Aza-Crown Ether or Morpholino Pendants in CTAB Micellar Solution

Two mono-Schiff base manganese (III) and cobalt (II) complexes with benzo-10-aza-crown ether pendants , and the analogous with morpholino pendants have been employed as models to mimic hydrolase in p-nitrophenyl picolinate (PNPP) in the buffered CTAB micellar solution. The kinetics and the mechanism on PNPP hydrolysis catalyzed by these complexes were investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed. The relative kinetic and thermodynamic parameters were determined. The effects of complexes structure and reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the rate for the catalytic PNPP hydrolysis was increased following the increase of pH of the buffered CTAB micellar solution; four complexes can efficiently accelerate the catalytic cleavage of PNPP in the buffered CTAB micellar solution. Compared with the crown-free analogous and , the crowned Schiff base complexes exhibit more high catalytic activity for promoting PNPP hydrolysis. The pseudo-first-order-rate ( k obs ) for the PNPP hydrolysis catalyzed by the complex in the CTAB micellar solution is 2.02 × 104 times than that of PNPP spontaneous hydrolysis in water at pH = 7.00, 25°C, [S] = 2.0 × 10−4 mol dm−3.

Hydrolysis of p‐Nitrophenyl Picolinate Catalyzed by Mono‐Schiff Base Complexes with Aza‐crown Ether or Morpholino Pendants

Abstract Mono‐Schiff base cobalt(II) and manganese(III) complexes with either benzo‐10‐aza‐crown ether pendants (CoL21, MnL21Cl) or morpholino pendants (CoL22, MnL22Cl) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p‐nitrophenyl picolinate (PNPP). The kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the rate increases with pH of the buffer solution and four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown‐free analogy CoL22 and MnL22Cl, the crowned Schiff base complexes (CoL21, MnL21Cl) exhibit higher catalytic activity. The pseudo‐first‐order‐rate (kobs) for the PNPP hydrolysis catalyzed by the complex MnL21Cl containing benzo‐10‐aza‐crown ether is 923‐fold higher than that of spontaneous hydrolysis of PNPP at pH=7.00, 25 °C, [S] =2.0×10−4 mol·dm−3.

Studies on p-nitrophenyl picolinate cleavage by mono-Schiff base complexes with aza-crown ether or morpholino pendants

Mono-Schiff base manganese(III) and cobalt(II) complexes with either benzo-10-aza-crown ether pendants (MnL1 2 Cl, CoL1 2) or morpholino pendants (MnL2 2Cl, CoL2 2) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP). A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have been also examined. The rate increases with pH of the buffer solution; all four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogues MnL2 2Cl and CoL2 2, the crowned Schiff base complexes (MnL1 2Cl, CoL1 2) exhibit higher catalytic activity. The pseudo-first-order-rate ( k obs ) for the PNPP hydrolysis catalyzed by the complex MnL1 2Cl containing benzo-10-aza-crown ether is 1.06 × 103 times that of spontaneous hydrolysis of PNPP at pH = 7.00, 25 °C, [S] = 2.0 × 10−4 mol dm−3. Studies on p-nitrophenyl picolinate cleavage by mono-Schiff base complexes with aza-crown ether or morpholino pendants Jian-zhang Li*, Fa-mei Feng, Bin Xu,Wei-dong Jiang Key Laboratory of Green and Technology, Department of Chemistry, Sichuan University of Science & Engineering, Zigong, Sichuan, 643000, P.R. China Sheng-ying Qin Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, P.R. China Mono-Schiff base manganese(III) and cobalt(II) complexes with either benzo-10-aza-crown ether pendants (MnL1 2Cl, CoL1 2) or morpholino pendants (MnL2 2Cl, CoL2 2) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with PNPP. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. Compared with the crown-free analogy MnL2 2Cl and CoL2 2, the crowned Schiff base complexes (MnL1 2Cl, CoL1 2) exhibit higher catalytic activity.

Hydrolysis of PNPP Catalyzed by Cu (II), Ni (II) Schiff Base Complexes in CTAB Micellar Solution

The kinetics of hydrolysis of p‐nitrophenyl picolinate(PNPP) catalyzed by metallomicelles formed from Cu (II), Ni (II) Schiff base complexes (CuL, NiL) and CTAB micelle were investigated in the pH range of 6.0–9.0 at 30°C. For the Cu (II) Schiff base complex CuL, the apparent rate constants (k obsd) of PNPP hydrolysis initially increased with the increasing pH of reaction media, then fell off. For the Ni (II) Schiff base complex NiL, the k obsd always increased with the increasing pH. The kinetic and thermodynamic parameters were calculated. The hydrolysis rate of PNPP catalyzed by Cu (II) complex was much larger than that by Ni (II) complex in CTAB micellar solution. The catalytic mechanism of the PNPP hydrolysis was discussed in detail, and the possibly active specie for the catalytic hydrolysis of PNPP was the monohydroxo metal complex.

Kinetic Study on p-Nitrophenyl Picolinate Hydrolysis Catalyzed by Metallomicelle

Abstract Two transition metal ion macrocyclic complexes, NiR and CuR (R: 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane perchloric acid), were synthesized and characterized. Metallomicelles made up of nickel (II) and copper (II) complexes with surfactant n -lauroyl sarcosinate were used as a mimetic hydrolytic metalloenzyme for catalytic hydrolysis of p -nitrophenyl picolinate (PNPP). The specific absorption spectra of the hydrolytic reaction systems indicated that the key intermediates made up of PNPP and Ni(II) or Cu(II) complex were formed during the reaction process. Based on the specific absorption spectra, the mechanism of PNPP catalytic hydrolysis was proposed, and a kinetic mathematical model was established. The results showed that the two metallomicelles exhibit high catalytic activity for the hydrolysis of PNPP. The catalytic hydrolysis of PNPP is an intramolecular nucleophilic substitution reaction, so the rate of the catalytic reaction is higher than that of spontaneous hydrolysis. The catalytic mechanism proposed is supported by the results of spectral analysis and the kinetic calculation. The structure of NiR and CuR is similar so that the difference in the catalytic activity between the two metallomicelles is less.

Studies on the Kinetics and Mechanism of Hydrolysis of p-nitrophenyl Picolinate (PNPP) by Unsymmetrical bis-Schiff Base Complexes with Aza-crown Ether or Morpholino Pendants

Two novel unsymmetrical bis-Schiff base manganese(III) and cobalt(II) complexes with benzo-10-aza-crown ether pendants (MnL1Cl, CoL1), and their analogoues with morpholino pendants (MnL2Cl, CoL2), have been synthesized and employed as models to mimic hydrolase in p-nitrophenyl picolinate (PNPP). The kinetics and the mechanism of PNPP hydrolysis catalyzed by these complexes were investigated. A kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed. The effects of the complexes structure and reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the rate for the catalytic PNPP hydrolysis increased following the increase in pH of the buffer solution; four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogoues MnL2Cl and CoL2, the crowned Schiff base complexes (MnL1Cl, CoL1) exhibit a higher catalytic activity; the pseudo-first-order-rate (kobs) for the PNPP hydrolysis catalyzed by the complex MnL1Cl containing benzo-10-aza-crown ether is 1.04 × 103 that of spontaneous hydrolysis of PNPP at pH = 7.00, [S] = 2.0×10−4 mol dm−3.

Kinetics and Mechanism of Hydrolysis of P-Nitrophenyl Picolinate by Transition-Metal Hydroxamate Containing Benzo-15-Crown-5

Two hydroxamic acids HL1 and HL2 containing benzo-15-crown-5 have been synthesised and their transition metal (Cu2+, Co2+, Zn2+, Mn2+) complexes have been employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate(PNPP). The kinetics and mechanism of PNPP hydrolysis have been investigated. A kinetic mathematical model of PNPP cleavage catalysed by these complexes is proposed. The effects of reactive temperature and metal ion in complexes on the rate of catalytic PNPP hydrolysis are discussed. The results show that the transition-metal hydroxamates (ML12, ML22, M= Cu2+, Co2+, Zn2+, Mn2+) containing benzo-15-crown-5 exhibit high activity in catalytic PNPP hydrolysis. The rate of PNPP hydrolysis catalysed by these complexes increased along with the increase of pH values of the buffer solution; the catalytic activity of different metal ions in complexes of the same ligand deceased in the order Cu2+> Co2+ >Zn2+ > Mn2+; the pseudo-first-order-rate constants of PNPP hydrolysis catalysed by the complexes are over 1000 times more than that of spontaneous hydrolysis of PNPP.

PNPP Hydrolysis Catalyzed by Manganese(III) Complexes with Crowned Salicylaldimine Schiff Base Ligand

Four manganese(III) complexes (MnL1Cl, MnL2Cl, MnL42Cl, MnL52Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL3Cl and MnL62Cl, the crowned Schiff base manganese(III) complexes, MnL1Cl, MnL2Cl, MnL42Cl and MnL52Cl, exhibit more high catalytic activity, which follow the order: MnL1Cl >MnL2Cl >MnL42Cl >MnL52Cl >MnL3Cl >MnL62Cl; the pseudo-first-order-rate (kobs) for the PNPP hydrolysis catalyzed by the complex MnL1Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL3Cl, 1.49 × 103 times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 × 10−4 mol dm−3.

Hydrolysis of p‐Nitrophenyl Picolinate Catalyzed by Mono‐ and Binuclear Transition Metal Complexes with Polyether Bridged Dihydroxamic Acid

AbstractTwo polyether bridged dihydroxamic acids and their mono‐ and binuclear manganese(II), zinc(II) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p‐nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono‐ and binuclear metal, the pseudo‐macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dihydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo‐macrocyclic polyether might synergetically activate H2O coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP.