Conformational studies of metal chelates. I. Intra-ring strain in five- and six-membered chelate rings

DeHayes, Louis J.; Busch, Daryle H.

doi:10.1021/ic50125a009

Cited by 76 publications

(24 citation statements)

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“…The force field parameters for bond lengths and bond angles of the Co(II)Sep model were adapted from Dehayes et al 36 and they are reported in 39 observed low and high spin state, respectively. Atomic partial charges were derived using the ChelpG scheme 40 with dipole moment constraint, and they are reported in Table S2 of SI.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Verma

Schwaneberg

Holtmann

et al. 2015

J. Chem. Theory Comput.

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One of the major limitations to exploit enzymes in industrial processes is their dependence on expensive reduction equivalents like NADPH to drive their catalytic cycle. Soluble electron transfer (ET) mediators like Cobalt(II)Sepulchrate have been proposed as a cost-effective alternative to shuttle electrons between an inexpensive electron source and enzyme redox center.The interactions of these molecules with enzymes are not elucidated at molecular level yet.

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Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Verma

Schwaneberg

Holtmann

et al. 2015

J. Chem. Theory Comput.

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“…Indeed, though tn ring may adopt different conformations, the most widely occurred is the least strained chair, with principal angles of 245" (16); this is exactly a mid-way position between 30" and -60" for isomers A and B.…”

Section: Aminopropyl Pendant Arms (Taptacn)mentioning

confidence: 99%

Metal ion complexes of 1,4,7-triazacyclononane and their aminoalkyl derivatives. Analysis of chelate rings fusion and molecular mechanics study

Pletnev¹

1994

Can. J. Chem.

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IGOR V. PLETNEV. Can. J. Chem. 72, 1404Chem. 72, (1994. Stereochemistry of metal ion complexes of 1,4,7-triazacyclononane, their N,Nf,N"-tris(aminoethyl), tris(aminopropyl), and their N,N'-(4,7-diazadecylene) derivatives is described in terms of the fusion of chelate rings at metal-nitrogen coordination bonds. Molecular mechanics calculations and analysis of the X-ray data confirm that the semi-quantitative analysis is valid and that fusion plays a critical role in the structure of the complexes. Molecular mechanics study of puckering of the ethylenediamine chelate ring, an essential part in this study, is also presented. IGOR V. PLETNEV. Can. J. Chem. 72, 1404Chem. 72, (1994.On dtcrit la stCrtochimie des complexes d'ions mCtalliques du 1,4,7-triazacyclononane et de ses dCrivCs N,N1,N"-tris(aminoethyl)-, tris(aminopropy1)-et N,N'-(4.7-diazadtcy1kne)-en fonctions de la fusion de noyaux chClates au niveau des liaisons de coordination mttal-azote. Des calculs de mtcanique moltculaire ainsi que des donntes de diffraction des rayons X confirment la validit6 d'une analyse semi-quantitative et prouvent le r61e critique que la fusion joue dans la structure des complexes. On prCsente aussi une Ctude de mCcanique molCculaire du plissement du cycle chtlatC de l'tthylknediamine qui est essentiel dans cette hypothkse.[Traduit par la Redaction] Introduction 1,4,7-Triazacyclononane (tacn) and its derivatives are known as versatile ligands. They are useful in the selective complexation and sequestering of metal ions, the stabilization of unusual oxidation states, magnetic resonance imaging, biomimicricy, etc. (for a review, see ref. 1; for some representative examples, see refs. 2-6). Stereochemistry of complexation plays a key role in all applications. Much is known about the stereochemistry from both experimental (1) and theoretical studies (e.g., molecular mechanics, MM calculations (7)).However, to understand the factors governing the stereochemical patterns, we believe one should focus on the fusion of the chelate rings in these complexes. Simple semi-quantitative analysis of how the conformation of one ring influence the conformation of the other and therefore the whole structure appears helpful in rationalizing the stereochemistry observed (8) and the molecular design (9).In this paper we attempt to apply this approach to conceptualise the stereochemical configurations in tacn complexes and their aminoalkyl derivatives (Fig. 1). MM calculations are used to investigate the puckering of an ethylenediamine chelate ring, which is a key subject in the consideration, and to refine the conformations predicted in polychelate systems.

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“…A number of results (6)(7)(8) indicate that the energy differences between conformers of fivemembered chelate rings are small. It has been shown (9) that the energy barriers to conformational inversion of these rings are also small.…”

Section: Theorymentioning

confidence: 99%

Variable Temperature Nuclear Magnetic Resonance Studies of Some Five-Membered Ring Chelate Complexes

Cullen¹,

Hall²,

Ward³

1975

Can. J. Chem.

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The temperature dependence of the n.m.r. spectra of nine ditertiary arsine chelate complexes of formula (CH3)2AsC(3)(3′)C(4) (4′)As(CH3)2M(CO)3X has been studied (M = Mo, Cr; X = CO; M = Mn; X = halogen; (3), (3′), (4), (4′) = H, F, Si(CH3)3, CN; but not all combinations ). Significant variation in coupling constants, indicating a shift in the conformer populations, was found only for the CHFCF2 bridged Mn(CO)3Cl complex, the CH2CF2 bridged Mn(CO)3Cl complex, and the CHFCHF bridged Mo(CO)4 complex. In the last case the 3JHH coupling constants were used to estimate ΔH ∼ 1 kcal/mol and ΔS ∼ 3 e.u for the conformational equilibrium.

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Conformational studies of metal chelates. I. Intra-ring strain in five- and six-membered chelate rings

Abstract: Conformational Studies of Metal Chelates tained from the same starting material under the neutral or basic conditions which permit the inversion of the configuration at the secondary N centers.

Cited by 76 publications

References 0 publications

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Metal ion complexes of 1,4,7-triazacyclononane and their aminoalkyl derivatives. Analysis of chelate rings fusion and molecular mechanics study

Variable Temperature Nuclear Magnetic Resonance Studies of Some Five-Membered Ring Chelate Complexes

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