Nitrogen-15 and carbon-13 NMR study of Roussin salts and esters and of pentacyanoferrate complexes

Butler, Anthony R.; Glidewell, Christopher; Hyde, Andrew; McGinnis, Joseph

doi:10.1021/ic00213a012

Cited by 57 publications

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“…Synthesis of isotopically labeled Na2[Fe( 13 CN5) 15 NO] was performed as previously reported by Hyde and co-workers 22,23 . We used the porous silica matrices synthesized during our previous study 15 and slowly performed impregnation with Na2[Fe( 13 CN5) 15 NO] during 48h to avoid any cracking.…”

Section: B) Sample Preparationmentioning

confidence: 99%

“…In addition to providing chemically resolved information, NMR is a suitable analysis technique to extract information about molecular dynamics [16][17][18][19] . First, by considering different nuclei ( 13 C, 23 Na, 1 H and 29 Si), it is easy to select the different species present in our system: NP anions, sodium counter-ions, water / silanols and the matrix respectively. In order to have reliable NMR measurements for evaluating the dynamics of these different species, SNP molecules were here selectively labeled for a better sensitivity.…”

Section: ) Introductionmentioning

confidence: 99%

“…In order to have reliable NMR measurements for evaluating the dynamics of these different species, SNP molecules were here selectively labeled for a better sensitivity. Secondly, from the dependence of longitudinal relaxation times (T1) of 13 C and 23 Na on temperature variations, motional activation energies can henceforth be obtained 20 . By comparing their respective values, correlation in the molecular tumbling of the different ionic species may step into the light.…”

Section: ) Introductionmentioning

confidence: 99%

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Bridging Structural and Dynamical Models of a Confined Sodium Nitroprusside Complex

et al. 2018

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Sodium nitroprusside (SNP), an active pharmaceutical ingredient, is encapsulated in biocompatible amorphous silica matrices and characterized by Solid-State NMR. We previously showed by complementary NMR and Pair Distribution Function (PDF) study, that when confined in 1-2nm sized nanopores of an amorphous silica matrix, the complex displays "liquid like" isotropic motion (NMR) but still retains an associated anion/cation preferential arrangement (PDF). In this study we present new insights on the physical state of the confined drug, in order to explain the coexistence of these two seemingly contradictory characteristics. By performing temperature-dependent T1 relaxation experiments on samples with different hydration levels, we retrieve respective motional activation energies for all three guest species inside the pores (Sodium cations, nitroprusside anions and water). For the hydrated samples we identify a temperature range where results ascertain isotropic but correlated ionic motion of the SNP ions. Contrastively, for the driest samples we detect NMR interactions that unravel adsorbed guest populations interacting with the pore surface. These descriptions of SNP dynamical properties clarify its unusually high ability to crystallize inside mesoporous matrices. * * * * * * * * * * * * * * * *

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Section: B) Sample Preparationmentioning

confidence: 99%

Section: ) Introductionmentioning

confidence: 99%

Section: ) Introductionmentioning

confidence: 99%

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Bridging Structural and Dynamical Models of a Confined Sodium Nitroprusside Complex

et al. 2018

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“…DNIC with i Pr bridging thiolate ligand was earlier studied by solution 15 N and 13 C NMR [42]. NMR data showed that [Fe 2 (l-SCHMe 2 ) 2 (NO) 4 ] exist in solution in two equimolar isomeric forms: cis-conformer (C 2v symmetry) and trans-conformer (C 2h symmetry).…”

Section: Theoretical Studiesmentioning

confidence: 99%

Synthesis and structure of dinitrosyl iron complexes with secondary thiolate bridging ligands [Fe2(μ-SCHR2)2(NO)4], R = Me, Ph

et al. 2015

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a b s t r a c tNew dinitrosyl iron complexes of binuclear structure [Fe 2 (l-SCHMe 2 ) 2 (NO) 4 ] and [Fe 2 (l-SCHPh 2 ) 2 (NO) 4 ] were first synthesized employing new method from Fe(CO) 5 , corresponding thiol, and EtONO. Complexes structures were determined by XRD technique. DFT calculations were performed to probe the cisconformer structures in gas and solution phases. NO donor ability of the complex with isopropyl thiolate ligand was studied.

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“…HCN is stored in solution as 7 , which reacts with NO 2 – (or NO 3 – ) to provide 8 . 37 HCN is also a source of CH 3 NH 2 9 , which is diazotized by 8 . Alkylation of 7 by 10 gives 12 and 11 .…”

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confidence: 99%

A Light-Releasable Potentially Prebiotic Nucleotide Activating Agent

et al. 2018

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Investigations into the chemical origin of life have recently benefitted from a holistic approach in which possible atmospheric, organic, and inorganic systems chemistries are taken into consideration. In this way, we now report that a selective phosphate activating agent, namely methyl isocyanide, could plausibly have been produced from simple prebiotic feedstocks. We show that methyl isocyanide drives the conversion of nucleoside monophosphates to phosphorimidazolides under potentially prebiotic conditions and in excellent yields for the first time. Importantly, this chemistry allows for repeated reactivation cycles, a property long sought in nonenzymatic oligomerization studies. Further, as the isocyanide is released upon irradiation, the possibility of spatially and temporally controlled activation chemistry is thus raised.

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Nitrogen-15 and carbon-13 NMR study of Roussin salts and esters and of pentacyanoferrate complexes

Cited by 57 publications

References 0 publications

Bridging Structural and Dynamical Models of a Confined Sodium Nitroprusside Complex

Bridging Structural and Dynamical Models of a Confined Sodium Nitroprusside Complex

Synthesis and structure of dinitrosyl iron complexes with secondary thiolate bridging ligands [Fe2(μ-SCHR2)2(NO)4], R = Me, Ph

A Light-Releasable Potentially Prebiotic Nucleotide Activating Agent

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