Regio-Directed Synthesis of a ZnIIFeIII Complex from an Unsymmetrical Ligand and Its Relevance to Purple Acid Phosphatases

Abstract

A new heterodinuclear Zn II Fe III µ-phenoxy complex has been prepared and isolated from the unsymmetrical ligand 2-{[bis(2-hydroxybenzyl)]amino}methyl-6-{[2-pyridinylmethyl)amino]methyl}-4-methylphenol (H 3 L 1 ), which provides two distinct N-and O-rich donor sets. The regioselective complexation is confirmed in solution by 1 H NMR studies (comparison of the spectra obtained from H 3 L 1 and HL 2 − a ligand with only the N-donor set available − and a zinc salt).

Metal Complexes of Organophosphate Esters and Open-Framework Metal Phosphates: Synthesis, Structure, Transformations, and Applications

“…The regioselective complexation of this ligand to Zn and Fe ions is confirmed in solution 1 H NMR studies. The crystal structure of 105 interestingly reveals that the observed NO 5 coordination sphere around the Fe III reproduces for the first time the O-rich coordination sphere around Fe III in KBPAP …”

Metal Complexes of Organophosphate Esters and Open-Framework Metal Phosphates: Synthesis, Structure, Transformations, and Applications

“…The regioselective complexation of this ligand to Zn and Fe ions is confirmed in solution 1 H NMR studies. The crystal structure of 105 interestingly reveals that the observed NO 5 coordination sphere around the Fe III reproduces for the first time the O-rich coordination sphere around Fe III in KBPAP …”

Asymmetric zinc(ii) complexes as functional and structural models for phosphoesterases

“…The 6 with the vinyl benzyl arm can be described as the 'monomer' of the immobilised complex. Moreover, the results presented herein suggest that incorporation of these types of complexes onto an insoluble supports, in this case Merrifield resin, results in a system exhibiting phosphoesterase activity.…”

Synthesis, Characterization, and Reactivity Studies of Heterodinuclear Complexes Modeling Active Sites in Purple Acid Phospatases

“…The bond between Fe(III) and the bridging phenolate is accordingly slightly shorter (0.05−0.03 Å) in 2 , 3 , and 4 as compared to the BPBPMP complexes. It is obvious, however, that the nature of the exogenous bridge(s) strongly influences the intermetal distance between the metals when comparisons are made to complexes with similar phenolate-bridging ligands as used here but different additional bridging moieties, for example, a hydroxide-bridged complex (Fe(III)−Zn(II) 3.040(1) Å), diphenylphosphate-bridged complexes (Fe(III)−Zn(II) 3.695(1) to 3.7402(7) Å), ,, a molybdate-bridged complex (Fe(III)−Zn(II) 3.819(4) Å) or complexes only containing the phenolate bridge and no exogenous bridge (3.5821(12); 3.828(1) Å).…”

Metal Complexes of Organophosphate Esters and Open-Framework Metal Phosphates: Synthesis, Structure, Transformations, and Applications

“…The regioselective complexation of this ligand to Zn and Fe ions is confirmed in solution 1 H NMR studies. The crystal structure of 105 interestingly reveals that the observed NO 5 coordination sphere around the Fe III reproduces for the first time the O-rich coordination sphere around Fe III in KBPAP …”

Asymmetric zinc(ii) complexes as functional and structural models for phosphoesterases

“…The 6 with the vinyl benzyl arm can be described as the 'monomer' of the immobilised complex. Moreover, the results presented herein suggest that incorporation of these types of complexes onto an insoluble supports, in this case Merrifield resin, results in a system exhibiting phosphoesterase activity.…”

Synthesis, Characterization, and Reactivity Studies of Heterodinuclear Complexes Modeling Active Sites in Purple Acid Phospatases

“…The bond between Fe(III) and the bridging phenolate is accordingly slightly shorter (0.05−0.03 Å) in 2 , 3 , and 4 as compared to the BPBPMP complexes. It is obvious, however, that the nature of the exogenous bridge(s) strongly influences the intermetal distance between the metals when comparisons are made to complexes with similar phenolate-bridging ligands as used here but different additional bridging moieties, for example, a hydroxide-bridged complex (Fe(III)−Zn(II) 3.040(1) Å), diphenylphosphate-bridged complexes (Fe(III)−Zn(II) 3.695(1) to 3.7402(7) Å), ,, a molybdate-bridged complex (Fe(III)−Zn(II) 3.819(4) Å) or complexes only containing the phenolate bridge and no exogenous bridge (3.5821(12); 3.828(1) Å).…”

Metal Complexes of Organophosphate Esters and Open-Framework Metal Phosphates: Synthesis, Structure, Transformations, and Applications

“…The regioselective complexation of this ligand to Zn and Fe ions is confirmed in solution 1 H NMR studies. The crystal structure of 105 interestingly reveals that the observed NO 5 coordination sphere around the Fe III reproduces for the first time the O-rich coordination sphere around Fe III in KBPAP …”

Asymmetric zinc(ii) complexes as functional and structural models for phosphoesterases

“…The 6 with the vinyl benzyl arm can be described as the 'monomer' of the immobilised complex. Moreover, the results presented herein suggest that incorporation of these types of complexes onto an insoluble supports, in this case Merrifield resin, results in a system exhibiting phosphoesterase activity.…”

Synthesis, Characterization, and Reactivity Studies of Heterodinuclear Complexes Modeling Active Sites in Purple Acid Phospatases

“…The bond between Fe(III) and the bridging phenolate is accordingly slightly shorter (0.05−0.03 Å) in 2 , 3 , and 4 as compared to the BPBPMP complexes. It is obvious, however, that the nature of the exogenous bridge(s) strongly influences the intermetal distance between the metals when comparisons are made to complexes with similar phenolate-bridging ligands as used here but different additional bridging moieties, for example, a hydroxide-bridged complex (Fe(III)−Zn(II) 3.040(1) Å), diphenylphosphate-bridged complexes (Fe(III)−Zn(II) 3.695(1) to 3.7402(7) Å), ,, a molybdate-bridged complex (Fe(III)−Zn(II) 3.819(4) Å) or complexes only containing the phenolate bridge and no exogenous bridge (3.5821(12); 3.828(1) Å).…”