Synthesis, X-ray Structure, Electrochemical, and EPR Studies of a Pentacoordinated Mn(II) Tetramethylcyclam Complex

Bucher, Christophe; Duval, Emmanuelle; Barbe, Jean‐Michel; Verpeaux, Jean‐Noël; Amatore, Christian; Guilard, Roger; Pape, Laurent Le; Latour, Jean‐Marc; Dahaoui, Slimane; Lecomte, Claude

doi:10.1021/ic001472h

Cited by 36 publications

(27 citation statements)

References 43 publications

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“…Geometry optimization and transition-states location were performed with the rational function optimization, RFO, [61,62] and the partitioned rational function optimization, P-RFO, [61] algorithms, respectively. [64] Results and Discussion…”

Section: Computational Detailsmentioning

confidence: 99%

“…To the best of our knowledge, no m-h 1 :h 1 Ni-O 2 -Mn complex has to date been isolated, the few examples containing this coordination correspond to dicopper, [25][26][27] dicobalt, [28][29][30] and [36] this work XR [64][a] this work XR [63] this work XR [36] this work [67] complexes. The NiÀO and MnÀO bond lengths in the intermediate, 2.01 and 2.09 , respectively, are found longer than the MÀO bond lengths in these Cu and Co compounds, which are in the range 1.87-1.95 .…”

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confidence: 99%

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On the Reaction Mechanism of the Complete Intermolecular O₂ Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

Zapata-Rivera¹,

Caballol²,

Calzado³

et al. 2014

Chemistry A European J

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The recently described intermolecular O2 transfer between the side-on Ni-O2 complex [(12-TMC)Ni-O2](+) and the manganese complex [(14-TMC)Mn](2+), where 12-TMC and 14-TMC are 12- and 14-membered macrocyclic ligands, 12-TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane and 14-TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long-range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two-step reaction, with a first rate-determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ-η(1):η(1)-O2 coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.

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Section: Computational Detailsmentioning

confidence: 99%

mentioning

confidence: 99%

On the Reaction Mechanism of the Complete Intermolecular O₂ Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

Zapata-Rivera¹,

Caballol²,

Calzado³

et al. 2014

Chemistry A European J

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“…SBA-15 is a mesoporous silicate generated from a non- 21 , in particular the tetra-Nsubstituted complexes 22,23 . Cyclam which is mono-tethered to the surface of SBA-15 displays a greater degree of metal uptake than di-or tetra-tethered cyclams 24 .…”

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confidence: 99%

Tailored adsorption of His₆-tagged protein onto nickel(ii)–cyclam grafted mesoporous silica

et al. 2010

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“…Cyclams can bind to a range of transition metals, including nickel, often achieving very high thermodynamic and kinetic stability in terms of metal ion dissociation which has lead to applications in catalysis [62] and medicine [63,64]. Ni-cyclam complexes have been extensively studied [65], in particular the tetra-N-substituted complexes [66,67]. Mono-N-substituted cyclam they exist in a trans-III (S, S, R, R) (square-planar) configuration with two accessible coordination sites above and below the plane of the ring [68], sites which can facilitate attachment of a protein to the surface of the silicate through a His 6 -tag on the protein (Scheme 1).…”

Section: Immobilisation Of Enzymes By Metal Affinity Methodsmentioning

confidence: 99%

Modification of Mesoporous Silicates for Immobilization of Enzymes

2012

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Mesoporous silicates (MPS) possess ordered pore structures with pore diameters sufficiently large to accommodate a range of enzymes. The successful immobilization of an enzyme on MPS usually requires modification of the surface of MPS to optimize the interactions between the support and the enzyme. Recent developments on the 2 functionalization of MPS for the immobilization of enzymes are described in this review.

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Synthesis, X-ray Structure, Electrochemical, and EPR Studies of a Pentacoordinated Mn(II) Tetramethylcyclam Complex

Cited by 36 publications

References 43 publications

On the Reaction Mechanism of the Complete Intermolecular O₂ Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

On the Reaction Mechanism of the Complete Intermolecular O₂ Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

Tailored adsorption of His₆-tagged protein onto nickel(ii)–cyclam grafted mesoporous silica

Modification of Mesoporous Silicates for Immobilization of Enzymes

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Synthesis, X-ray Structure, Electrochemical, and EPR Studies of a Pentacoordinated Mn(II) Tetramethylcyclam Complex

Cited by 36 publications

References 43 publications

On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

Tailored adsorption of His6-tagged protein onto nickel(ii)–cyclam grafted mesoporous silica

Modification of Mesoporous Silicates for Immobilization of Enzymes

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Product

Resources

About

On the Reaction Mechanism of the Complete Intermolecular O₂ Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

On the Reaction Mechanism of the Complete Intermolecular O₂ Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

Tailored adsorption of His₆-tagged protein onto nickel(ii)–cyclam grafted mesoporous silica