Imidazole-Ligated Copper Complexes: Synthesis, Structure, and Reactivity

Sorrell, Thomas N.; Garrity, M. L.; Richards, Joseph L.; Pigge, F. Christopher; Allen, William E.

doi:10.1007/978-94-011-6875-5_26

Cited by 3 publications

(3 citation statements)

References 30 publications

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“…[5] In general, the electronic structures of pyridinyl, pyrazolyl or imidazolyl complexes differ strongly due to the differences in σ and π donor abilities. [6][7][8][9] severe disorders between pyrazolyl and pyridinyl donor groups are observed such that bis(pyrazolyl) and (pyrazolyl)(pyridinyl) coordination modes are concomitantly found. The donor competition is dissected by DFT calculation of the energy differences between the two coordination modes and NBO analysis of the donor situation.…”

Section: Introductionmentioning

confidence: 99%

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Dissection of Different Donor Abilities Within Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes

Hoffmann

Herres‐Pawlis

2013

Zeitschrift anorg allge chemie

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Using the bis(pyrazolyl)pyridinylmethane ligand α,α,α-bis(1-pyrazolyl)(2-pyridinyl)toluene {(ph)C(pz) 2 (py)} for bioinorganic inspired coordination chemistry studies, we synthesised and structurally characterised three monofacial complexes [{(ph)C(pz) 2 (py)}CoCl 2 ] (C1), [{(ph)C(pz) 2 (py)}CuCl 2 ] (C2), [{(ph)C(pz) 2 (py)}ZnCl 2 ] (C3) and the binuclear halogenidobridged complexes [{(ph)C(pz) 2 (py)} 2 (μ-Cl) 2 Fe 2 Cl 2 ] (C4) and [{(ph)C(pz) 2 (py)} 2 (μ-Br) 2 Cu 2 Br 2 ] (C5). In four of these complexes, * Prof. Dr. S. Herres-Pawlis

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Section: Introductionmentioning

confidence: 99%

“…With regard to π donor abilities, pyrazolyl is superior to pyridinyl as well 5. In general, the electronic structures of pyridinyl, pyrazolyl or imidazolyl complexes differ strongly due to the differences in σ and π donor abilities 6–9…”

Section: Introductionmentioning

confidence: 99%

Dissection of Different Donor Abilities Within Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes

Hoffmann

Herres‐Pawlis

2013

Zeitschrift anorg allge chemie

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“…Substantial rate accelerations for hydrolysis, particularly of carboxylic acid esters, have been attained with some of these model Cu(II) and Zn(II) complexes (33)(34)(35)(36). Although Cu complexes, which reasonably mimic the structural and spectroscopic features of the Cu-hydroxylases, have been prepared (37)(38)(39)(40), few possess polyimidazole ligands or have been shown to promote the hydroxylation of relevant substrates (usually stoichiometric hydroxylation of their own ligands is a major problem) (41)(42)(43)(44), and none of these reactions are catalytic.…”

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confidence: 99%

A cofactor approach to copper-dependent catalytic antibodies

Nicholas

Wentworth

Harwig

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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A strategy for the preparation of semisynthetic copper(II)-based catalytic metalloproteins is described in which a metal-binding bis-imidazole cofactor is incorporated into the combining site of the aldolase antibody 38C2. Antibody 38C2 features a large hydrophobic-combining site pocket with a highly nucleophilic lysine residue, Lys H93 , that can be covalently modified. A comparison of several lactone and anhydride reagents shows that the latter are the most effective and general derivatizing agents for the 38C2 Lys residue. A bis-imidazole anhydride (5) was efficiently prepared from N-methyl imidazole. The 38C2-5-Cu conjugate was prepared by either (i) initial derivatization of 38C2 with 5 followed by metallation with CuCl 2, or (ii) precoordination of 5 with CuCl 2 followed by conjugation with 38C2. The resulting 38C2-5-Cu conjugate was an active catalyst for the hydrolysis of the coordinating picolinate ester 11, following Michaelis-Menten kinetics [kcat(11) ‫؍‬ 2.3 min ؊1 and Km(11) 2.2 mM] with a rate enhancement [k cat(11)kuncat (11) C atalysis at metal centers plays a key role in both enzymatic and abiological reactions, providing reaction pathways, rates, and selectivity often unattainable from conventional acid, base, or nucleophilic catalysis. However, traditionally separate disciplines, the study of natural (i.e., enzymatic) and synthetic (nonbiological) catalysts has interfaced with the genesis of semisynthetic and de novo proteins (1). A number of methods have been explored for producing such hybrid species that possess metal centers, including: (i) attachment of a synthetic metal-containing cofactor to a protein (2-4); (ii) antibody elicitation using a metal-binding hapten͞protein conjugate (5-10); (iii) site-directed mutagenesis of proteins and antibodies to incorporate metal-binding sites (11-15); and (iv) panning of antibody libraries for metal binding using immobilized metal complexes (16,17).Our approach is directed toward the design and generation of novel metallo-catalytic antibodies and is inspired by the active-site structures of the many metalloenzymes that possess a coordination sphere with two or more histidine-derived imidazole ligands. The most important catalytic functions of such polyhistidyl enzymes are hydrolytic or oxidative. Illustrative of the numerous and structurally diverse polyhistidyl Zn-hydrolases (18) is carboxypeptidase A, which catalyzes the hydrolysis of C-terminal amino acid residues and features a bis-histidine͞glutamate (CO 2 Ϫ ) coordination sphere and the nucleophilic assistance of a nearby Glu (19). The Cuhydroxylases, dopamine ␤-hydroxylase and peptide amidating hydroxylase (20), are chemically extraordinary in effecting the regio-and enantioselective hydroxylation of weakly activated COH bonds, a transformation with little precedent among nonenzymatic copper catalysts (21,22). The active sites of hydroxylase enzymes possess two Cu-polyhistidine centers, one of which appears to serve as an electron or superoxide transfer site and the other at which the substra...

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ChemInform Abstract: Imidazole‐Ligated Copper Complexes: Synthesis, Structure, and Reactivity

Sorrell¹,

Garrity²,

Richards³

et al. 1995

ChemInform

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Imidazole-Ligated Copper Complexes: Synthesis, Structure, and Reactivity

Cited by 3 publications

References 30 publications

Dissection of Different Donor Abilities Within Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes

Dissection of Different Donor Abilities Within Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes

A cofactor approach to copper-dependent catalytic antibodies

ChemInform Abstract: Imidazole‐Ligated Copper Complexes: Synthesis, Structure, and Reactivity

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Imidazole-Ligated Copper Complexes: Synthesis, Structure, and Reactivity

Cited by 3 publications

References 30 publications

Dissection of Different Donor Abilities Within Bis(pyrazolyl)­pyridinylmethane Transition Metal Complexes

Dissection of Different Donor Abilities Within Bis(pyrazolyl)­pyridinylmethane Transition Metal Complexes

A cofactor approach to copper-dependent catalytic antibodies

ChemInform Abstract: Imidazole‐Ligated Copper Complexes: Synthesis, Structure, and Reactivity

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Dissection of Different Donor Abilities Within Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes

Dissection of Different Donor Abilities Within Bis(pyrazolyl)pyridinylmethane Transition Metal Complexes