A molecular mechanics study of dioxygen binding by lacunar cobalt dioxygen carriers

Lin, Wang Kan; Alcock, Nathaniel W.; Busch, Daryle H.

doi:10.1021/ja00020a023

Cited by 39 publications

(17 citation statements)

References 4 publications

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“…A considerable amount of time was given to the location of viable (continued). (c) Complex 9; the donor atoms used are C=O (1), C=O(7), N(14), N (17), C=O(30) andOAc (32) to give the metal stereochemistry as 0C-6-25-A. (d) Complex 10; the donor atoms used are as for (c), but the metal stereochemistry is 0C-6-25-C.…”

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confidence: 99%

Stereochemistry of ulapualides, a new family of tris-oxazole-containing macrolide ionophores from marine nudibranchs. A molecular mechanics study

Maddock

Pattenden

Wight

1993

J Computer-Aided Mol Des

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A molecular mechanics study of the marine metabolite ulapualide A, which is suggested to have ionophoric properties, has been carried out on various metal chelated complexes in order to predict the stereochemistry of the natural product. The results suggest a stereochemistry for ulapualide A which is closely similar to structurally related marine metabolites, whose stereochemistries have been established by X-ray crystallography and by partial synthesis.

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confidence: 99%

Stereochemistry of ulapualides, a new family of tris-oxazole-containing macrolide ionophores from marine nudibranchs. A molecular mechanics study

Maddock

Pattenden

Wight

1993

J Computer-Aided Mol Des

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“…74 Molecular mechanics and molecular dynamics calculations also support the accessibility of a saddle-shaped geometry in 15-membered cyclidenes and related molecules and a predominantly planar conformation of the 14-membered complexes. 55,56, 115 The ethylpyridine arms were expected to be the most flexible parts of the complexes I-III. This assumption was confirmed by both X-ray crystallography and NMR.…”

Section: Discussionmentioning

confidence: 99%

Nickel(II) Cyclidenes with Appended Ethylpyridine Receptor Centers as Molecular Tweezers for Dicarboxylic Acids

et al. 2003

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A series of 14-, 15-, and 16-membered nickel(II) cyclidene macrocycles appended with 2-aminoethyl(2-pyridine) receptors I-III, respectively, were prepared and characterized by X-ray crystallography and NMR techniques. The 14- and 15-membered macrocycles I and II exist in a planar or extended Z-configuration, whereas the 16-membered macrocycle III was saddle shaped and had two asymmetric configurations in the unit cell (IIIa in a "capped" configuration and IIIb in an "open" configuration). Variable-temperature (1)H NMR studies of III in CD(3)CN were conducted (25-65 degrees C), and at room temperature, the interconversion between capping and uncapping is slow on the NMR time scale, resulting in a broad spectrum, whereas at 65 degrees C, interconversion was fast. (1)H NMR binding studies indicated I-III bind unsaturated dicarboxylic acids in a 1:1 stoichiometry with binding constants approaching 400 M(-)(1) in CD(3)CN, and the binding strength was dependent on the shape of the macrocyclic cyclidene platforms, whereas monocarboxylic acids were not bound. Generally, the planar 14-membered cyclidene I bound diacids the weakest and the 16-membered cyclidene III bound diacids the strongest. The presence of nuclear Overhauser effect spectrometry cross peaks in a 20 mM solution of 1:1 II-maleic acid indicates that the binding mode is ditopic with the guest being encapsulated by the aminoethylpyridine arms above the macrocyclic framework.

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“…The length and anchor position of the polymethylene chain can expose or “hide” a reactive site of a compound (Scheme 3). In 1980, Busch et al [44, 45] showed that the chain of length six (rather than five) methylenes increased the affinity of oxygen in cobalt cyclidene 7 , which formed a CoO 2 adduct. In 1980, Marshall [32] showed that unlike trans -fused 9 , cis-fused 8 forms a colored charge-transfer complex with tetracyano-ethylene (TCNE) due to its less shielded alkene site.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies of a singlet oxygen-releasing dioxapaddlane (1,4-diicosa naphthalene-1,4-endoperoxide)

Castillo

Greer

2009

Struct Chem

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Theoretical calculations have been used to examine singlet oxygen release from a naphthalene endoperoxide which bears a flexible (CH2)22 polymethylene “lid”. Monte Carlo and ONIOM calculations that incorporated semi-empirical and density functional theory predicted the conformational influence of the polymethylene chain in the cycloreversion of dioxapaddlane, 1,4-diicosa naphthalene-1,4-endoperoxide, to 1O2 and 1,4-diicosa naphthalene. This study attempts to build a connection between 1O2 generation and “jump rope” dynamics of the dioxapaddlane. The polymethylene chain appears to function as a gatekeeper for the oxygen. Instead of coming full circle, a semi-circle rotation of the polymethylene bridge protected the peroxide group, limiting the dissociation of 1O2 from the naphthalene site.

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A molecular mechanics study of dioxygen binding by lacunar cobalt dioxygen carriers

Cited by 39 publications

References 4 publications

Stereochemistry of ulapualides, a new family of tris-oxazole-containing macrolide ionophores from marine nudibranchs. A molecular mechanics study

Stereochemistry of ulapualides, a new family of tris-oxazole-containing macrolide ionophores from marine nudibranchs. A molecular mechanics study

Nickel(II) Cyclidenes with Appended Ethylpyridine Receptor Centers as Molecular Tweezers for Dicarboxylic Acids

Theoretical studies of a singlet oxygen-releasing dioxapaddlane (1,4-diicosa naphthalene-1,4-endoperoxide)

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