Synthesis and Spectroscopic Characterisation of a Heterodinuclear Iron(III)‐Copper(II) Complex Based on an Asymmetric Dinucleating Ligand System

Heims, Florian; Mereacre, Valeriu; Ciancetta, Antonella; Mebs, Stefan; Powell, Annie K.; Greco, Claudio; Ray, Kallol

doi:10.1002/ejic.201200156

Cited by 10 publications

(30 citation statements)

References 34 publications

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“… Examples of dinucleating ligands for the synthesis of heterodinuclear complexes as structural models of PAP: (a), [12c,12d,12m–12o,12q] (b),44 (c),13a (d),12g,13b (e),12a (f),12a,42 (g),23e (h),12i (i),23d (j),12b,19 (k),11a (l) 11c…”

Section: Introductionmentioning

confidence: 99%

A Heterodinuclear Fe^IIIZn^II Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific Zn^II Binding

2015

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Purple acid phosphatases (PAPs) are the only dinuclear metallohydrolases for which the necessity for a heterovalent active site (Fe III -M II ; M = Fe, Zn or Mn) for catalysis has been established. A major goal for the synthesis of PAP biomimetics is to design a ligand in which the two coordination sites exhibit discrimination between the trivalent and divalent metal ions. With this goal in mind the ligand 2-{[bis(2-methoxyethyl)amino]methyl}-6-{[(2-hydroxybenzyl)(2-pyridylmethyl)amino]methyl}-4-methylphenol (BMMHPH 2 ), with two distinct coordination sites, N 2 O 2 (α) and NO 3 (β), has been prepared. Although not exactly mimicking the active site of PAP, the ligand facilitated the formation of the complex [Fe III Zn II (BMMHP)(CH 3 COO) 2 ](BPh 4 ), which exhibited regioselectivity in the two metal binding sites. The phos-

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Section: Introductionmentioning

confidence: 99%

A Heterodinuclear Fe^IIIZn^II Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific Zn^II Binding

2015

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“…Fe–O bond lengths in 1 vary in the range of 1.834(4)–2.004(4) Å, whereas the Fe–N bonds are generally longer [2.133(4)–2.249(5) Å]. For the Cu–O and Cu–N bonds similar trends are found [1.965(4)–1.976(4) Å for Cu–O and 2.014(5)–2.183(4) Å for Cu–N] . The trend of shorter Fe–O and longer Fe–N distances is also observed in 2 – 5 .…”

Section: Resultsmentioning

confidence: 53%

“…These heterodinuclear active sites can exhibit alternative reactivity patterns relative to their symmetric counterparts. Hence, the synthesis and the understanding of the reactivity properties of heterodimetallic complexes are important in the context of modelling the structures and reactivities of metalloenzymes containing two different metal ions at their active sites . However, such studies are not trivial due to the challenges associated with synthesis of heterodinuclear complexes, mainly because of the possibility of disproportionation and the formation of mixtures of homo‐ and heterodinuclear complexes, as well as metal‐site isomers.…”

Section: Introductionmentioning

confidence: 99%

“…However, such studies are not trivial due to the challenges associated with synthesis of heterodinuclear complexes, mainly because of the possibility of disproportionation and the formation of mixtures of homo‐ and heterodinuclear complexes, as well as metal‐site isomers. A limited number of successful synthesis of heterodinuclear complexes involve the use of asymmetric ligands that bind metals selectively in one pocket or strongly enough to prevent disproportionation and metal mixing , …”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Reactivity of a Series of Homo‐ and Hetero‐dinuclear Complexes based on an Asymmetric FloH Ligand System

Battistella

Heims

Braun‐Cula

et al. 2020

Zeitschrift anorg allge chemie

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In a previous communication we reported the site‐directed generation of a heterodinuclear FeIIICuII complex (1) by using an asymmetric dinucleating ligand FloH. The iron(III) ion was introduced first on the preferential metal‐binding site of the ligand that led to the formation of the thermodynamically favored five‐membered chelate ring upon metal‐binding. Copper(II) was introduced in the next step. The stepwise metalation strategy reported previously has now been extended to synthesize a series of heterodinuclear FeIIIMII [M = Mn (2), Fe (3), Co (4), and Ni (5)] and FeIICuI (1a) as well as the homodinuclear CuICuI (6) complexes. The complexes were characterized by X‐ray crystallography (except for 1a and 6), and by a limited number of spectroscopic methods. Complex 1 with a labile solvent binding site at FeIII reacted with H2O2 to form a transient intermediate that showed reactivity typical of metal peroxide complexes. The metal centers in the complexes 2–5 are coordinatively saturated, and hence they showed no reactivity with H2O2. Complex 1a reacted with O2 via an intermolecular pathway to form a μ‐oxo bridged tetrameric complex 1b, which was structurally characterized. This is in contrast to the homodinuclear CuICuI and heme FeIICuI cores, which prefer an intramolecular pathway for O2 activation.

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“…Various ligands both of the symmetrical [39][40][41][42][43][44][45][46][47][48][49] and unsymmetrical [31,42,[50][51][52][53][54][55][56][57] [90] types have been reported in literature. In this regard, we intend to design synthetic mimics of the dinucleating enzymes namely, PAP and zinc phosphoesterase using a symmetrical ligand containing a phenoxy bridge and tetra pyridine side arms.…”

Section: Accepted Manuscript Introductionmentioning

confidence: 99%

Heterodinuclear Zn(II)−Fe(III) and Homodinuclear M(II)−M(II) [M = Zn and Ni] complexes of a Bicompartmental [N 6 O] ligand as synthetic mimics of the hydrolase family of enzymes

Pathak

Kumar

Gangwar

et al. 2018

Journal of Inorganic Biochemistry

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Heterodinuclear mixed valence [Zn(II)-Fe(III)] and the homodinuclear [Zn(II)-Zn(II)] and [Ni(II)-Ni(II)] complexes of a bicompartmental ligand containing a bridging phenoxy as a O-donor and four pyridyl moieties and two amine moieties as the N-donors exhibit phosphoester hydrolysis activity similar to the hydrolase family of enzymes. While the heterodinuclear [Zn(II)-Fe(III)] (2) complex was obtained by the sequential addition of Fe(NO)∙9HO and Zn(OAc)∙2HO to the ligand 2,6‑bis{[bis(2‑pyridylmethyl)amino]methyl}‑4‑t‑butylphenol (HL) (1) in moderate yield of 37%, the homodinuclear [Zn(II)-Zn(II)] (3) and [Ni(II)-Ni(II)] (4) complexes were obtained by the direct reaction of the ligand (1) with Zn(OAc)∙2HO and Ni(OAc)∙2HO respectively, in good to moderate yields (43-63%). Based on the spectrophotometric titration and the mass spectrometry studies, a monoaquated and dihydroxo species 2C, 3C and 4C has been identified as the catalytically active species responsible for the phosphodiester hydrolysis of the bis(2,4 - dinitrophenyl)phosphate (2,4 - BDNPP) substrate in the pH range 5.5-10.5. The kinetic studies further revealed that the homodinuclear [Ni(II)-Ni(II)] complexes (4) (k = 1.26 × 10 s) is more active by 39 times than the homodinuclear [Zn(II)-Zn(II)] complexes (3) (k = 3.20 × 10 s) and 27 times more active than the heterodinuclear [Zn(II)-Fe(III)] complex (2) (k = 4.62 × 10 s) in the phosphodiester hydrolysis activity. Significantly enough, the catalyst-substrate adduct species (2E, 2F and 3F) containing a metal bound bis(2,4‑dinitrophenyl)phosphate has been detected by mass spectrometry for the first time.

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Synthesis and Spectroscopic Characterisation of a Heterodinuclear Iron(III)‐Copper(II) Complex Based on an Asymmetric Dinucleating Ligand System

Cited by 10 publications

References 34 publications

A Heterodinuclear Fe^IIIZn^II Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific Zn^II Binding

A Heterodinuclear Fe^IIIZn^II Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific Zn^II Binding

Synthesis, Characterization, and Reactivity of a Series of Homo‐ and Hetero‐dinuclear Complexes based on an Asymmetric FloH Ligand System

Heterodinuclear Zn(II)−Fe(III) and Homodinuclear M(II)−M(II) [M = Zn and Ni] complexes of a Bicompartmental [N 6 O] ligand as synthetic mimics of the hydrolase family of enzymes

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Synthesis and Spectroscopic Characterisation of a Heterodinuclear Iron(III)‐Copper(II) Complex Based on an Asymmetric Dinucleating Ligand System

Cited by 10 publications

References 34 publications

A Heterodinuclear FeIIIZnII Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific ZnII Binding

A Heterodinuclear FeIIIZnII Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific ZnII Binding

Synthesis, Characterization, and Reactivity of a Series of Homo‐ and Hetero‐dinuclear Complexes based on an Asymmetric FloH Ligand System

Heterodinuclear Zn(II)−Fe(III) and Homodinuclear M(II)−M(II) [M = Zn and Ni] complexes of a Bicompartmental [N 6 O] ligand as synthetic mimics of the hydrolase family of enzymes

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A Heterodinuclear Fe^IIIZn^II Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific Zn^II Binding

A Heterodinuclear Fe^IIIZn^II Complex as a Mimic for Purple Acid Phosphatase with Site‐Specific Zn^II Binding

Heterodinuclear Zn(II)−Fe(III) and Homodinuclear M(II)−M(II) [M = Zn and Ni] complexes of a Bicompartmental [N 6 O] ligand as synthetic mimics of the hydrolase family of enzymes