Adducts of rhodium(II) tetraacylates with methionine and its derivatives: 1H and 13C nuclear magnetic resonance spectroscopy and chiral recognition

Głaszczka, Rafał; Jaźwiński, Jarosław; Kamieński, Bohdan; Kamińska, M.

doi:10.1016/j.tetasy.2010.08.010

Cited by 17 publications

(20 citation statements)

References 31 publications

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“…Coupled with the optical spectroscopic data, we identify the cysteine sulfur as being the donor atom from the GSH that is involved. The GSbinds to the vacant axial position of Rh2(OAc)4 that is generally coordinated by solvent, as is confirmed by similar studies concerning dirhodium complexes 37,39 .…”

Section: Elucidating Qualitative Spectroscopic Results With Quantitatsupporting

confidence: 75%

“…1) which has been historically associated with a S(σ) →Rh(σ*) ligand-to-metal-charge transfer band (LMCT) characteristic of sulfur coordination to dirhodium carboxylates. A similar band has been previously reported for the spectrum of Rh2(OAc)4 coordinated to the cysteine-rich protein, metallothionein 37,39,48 . As we will discuss below, this assignment was found to be a mixture of molecular orbitals Please do not adjust margins Please do not adjust margins (MO) involving both the Rh-Rh MOs and the thiolate orbitals.…”

Section: Uv-visible and Circular Dichroism Spectroscopy Following Thesupporting

confidence: 86%

“…Dirhodium(II) carboxylates and their derivatives are an emerging class of anti-tumour compounds that are described as exhibiting greater potency than cisplatin in vitro [32][33][34][35][36][37][38] . However, significantly, with respect to possible cellular chemistry, rhodium(II) carboxylates bind strongly to sulfur containing compounds 32,33,35,37,[39][40][41] . Indeed, the propensity for these rhodium complexes to deplete intracellular thiols makes them especially useful as radiosensitizers 42,43 .…”

Section: Introductionmentioning

confidence: 99%

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Glutathione binding to dirhodium tetraacetate: a spectroscopic, mass spectral and computational study of an anti-tumour compound

et al. 2017

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a See AcknowledgementsGlutathione (γ-L-glutamyl-L-cysteinyl-glycine) is a ubiquitous tripeptide found in all plants and animals. While a major participant in many biological reactions, glutathione has key roles as a metallochaperone, in the reduction of oxidative stress, in the transport of metabolites, and as a cellular thiol source. Here, we report its reaction with , dirhodium(II) tetraacetate (Rh2(OAc)4), a compound with anti-tumour properties, using electrospray ionization mass spectrometry and spectroscopic methods to observe in depth the stoichiometries of the final conjugate. Using computational analysis, we provide the first report of the orbital assignments for the resulting glutatathione-bound product. We also explore the competition by GSH for methionine-bound sites on Rh2(OAc)4 as a method for possible protection of its cellular-based therapeutic activity.

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Section: Elucidating Qualitative Spectroscopic Results With Quantitatsupporting

confidence: 75%

Section: Uv-visible and Circular Dichroism Spectroscopy Following Thesupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

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Glutathione binding to dirhodium tetraacetate: a spectroscopic, mass spectral and computational study of an anti-tumour compound

et al. 2017

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“…On contrast, in case of complex 32b it reduces the dispersion effect value ( ); as a consequence, this complex is unqualified to be used as a chiral auxiliary. G aszczka et al [104] have also studied the complexation effects of different rhodium(II) dimeric tetraacylates (i.e., tetraacetate [Rh 2 (OAc) 4 (Fig. 29) which was investigated by means of 1 H and 13 C NMR and absorption electronic spectroscopy in the visible range.…”

Section: Elucidation By Formation Of Adductsmentioning

confidence: 99%

Chiral Dirhodium Catalysts: A New Era for Asymmetric Catalysis

El‐Deftar¹,

Adly²,

Gardiner

et al. 2012

COC

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The catalysis by dirhodium paddlewheel complexes has been an area of immense interest and extensive study over the past three decades -not only because most of the catalysts are highly stable to heat, moisture and ambient atmosphere but also for the asymmetric induction in the ylide generation. In this review, we attempt to provide an overview on the general preparation method for most homogeneous chiral dirhodium(II) catalysts that have appeared to date and their recent applications in asymmetric catalysis with iodonium ylides as carbenoid precursors.

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“…Previously, we investigated the interactions of rhodium tetracarboxylates with organic ligands bearing N, O, and S atoms . Depending on experimental conditions (slow or fast ligand exchange rate on the NMR timescale), we observed either the individual signals of ligand and adduct or the signals at averaged positions.…”

Section: Introductionmentioning

confidence: 99%

Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations

Cmoch

Głaszczka

Jaźwiński

et al. 2013

Magnetic Reson in Chemistry

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Complexation of tetrakis(μ2-N,N'-diphenylformamidinato-N,N')-di-rhodium(II) with ligands containing nitrile, isonitrile, amine, hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups has been studied in liquid and solid phases using (1)H, (13)C and (15)N NMR, (13)C and (15)N cross polarisation-magic angle spinning NMR, and absorption spectroscopy in the visible range. The complexation was monitored using various NMR physicochemical parameters, such as chemical shifts, longitudinal relaxation times T1 , and NOE enhancements. Rhodium(II) tetraformamidinate selectively bonded only unbranched amine (propan-1-amine), pentanenitrile, and (1-isocyanoethyl)benzene. No complexation occurred in the case of ligands having hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups, and more expanded amine molecules such as butan-2-amine and 1-azabicyclo[2.2.2]octane. Such features were opposite to those observed in rhodium(II) tetracarboxylates, forming adducts with all kind of ligands. Special attention was focused on the analysis of Δδ parameters, defined as a chemical shift difference between signal in adduct and corresponding signal in free ligand. In the case of (1)H NMR, Δδ values were either negative in adducts of rhodium(II) tetraformamidinate or positive in adducts of rhodium(II) tetracarboxylates. Experimental findings were supported by density functional theory molecular modelling and gauge independent atomic orbitals chemical shift calculations. The calculation of chemical shifts combined with scaling procedure allowed to reproduce qualitatively Δδ parameters.

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Adducts of rhodium(II) tetraacylates with methionine and its derivatives: 1H and 13C nuclear magnetic resonance spectroscopy and chiral recognition

Cited by 17 publications

References 31 publications

Glutathione binding to dirhodium tetraacetate: a spectroscopic, mass spectral and computational study of an anti-tumour compound

Glutathione binding to dirhodium tetraacetate: a spectroscopic, mass spectral and computational study of an anti-tumour compound

Chiral Dirhodium Catalysts: A New Era for Asymmetric Catalysis

Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations

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