Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]- Building Block Via Solid-State NMR Spectroscopy, Polarized Neutron Diffraction, and First-Principle Calculations

International audienceThe local magnetic structure in the [Fe (Tp)(CN) ] building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions

A quinhydrone-type 2 ∶ 1 acceptor–donor charge transfer complex obtained via a solvent-free reaction

International audienceA 2 ∶ 1 2-methoxybenzoquinone (BQOMe)–hydroquinone (H2Q) complex (5), obtained as single crystals by a solvent-free reaction, combines dipolar and π–π interactions, as well as hydrogen bonding

Barium one-dimensional coordination polymers from barium β-diketonates and 2,2′-bipyrimidine derivatives

International audienc

Adoption of Macy Catheter by Aurora at Home hospice staff: A quality improvement evaluation study

Background: The Macy Catheter (MC) is a tool to aid rectal delivery of oral medications in microenemas. In 2019, Aurora Health at Home hospice chose the MC as a preferred route for delivery of medications when patients no longer tolerate the oral route. Despite training, adoption of the MC has been slow. Purpose: To determine what barriers exist to faster adoption and utilization of the MC by hospice nursing staff. It is anticipated that once the barriers are identified they will be addressed through a campaign of quality improvement projects with subsequent monitoring of adoption. Methods: An anonymous survey was given to 28 nurses at 2 meetings. The survey identified nurses that used the MC and their experiences. Nurses who had not used it were queried to see if they had no eligible patients or, if they had eligible patients, what their reasons were for not using it. Demographic data included age, experience as a registered nurse (RN) and hospice RN, usual shift worked, and work status. Basic descriptive statistics were used to describe the population. Results: Of a total of 28 surveys completed, 7 reflected use of the MC, with most using it only once and 1 using it 3–5 times. The number of medication doses given ranged from 1 to 10–20. There was an overall agreement regarding the ease of the MC insertion and its effectiveness when compared to the oral route. There were no complications noted. Ten nurses reported to never have used the MC because of not having eligible patients, while 12 reported having eligible patients and not using the MC, though 9 considered it. Common reasons for not using it include patient/family objections, inexperience using the MC, or confidence in other methods. One nurse reported not using it due to a nursing facility policy. Of those who had eligible patients and who did not consider using it, reasons given included unfamiliarity and not thinking of it in the “heat of the moment.” There were no demographic differences among these groups that would account for their willingness to use or consider the MC. Conclusion: The study identified leadership opportunities to increase the use of the Macy Catheter. Experienced nurses can help train and teach their peers how to “sell” this device to patients, families, and other clinicians. There is a need to develop educational collateral to help families understand the utility of the MC. We can work with facilities to make sure their policies align with the latest nursing approaches for excellent hospice care

Self-organization of the 2-methoxyquinhydrone charge transfer complex in polar planes

International audiencePolar planes resulting from the association of polar stacks through hydrogen bonds, have been evidenced on single crystals of a substituted quinhydrone prepared by a one-pot oxidation-co-sublimation solvent-free process

Asymmetric Synthesis of the Oxygenated Polycyclic System of (+)-Harringtonolide

A straightforward asymmetric synthesis of the cage oxygenated structure of (+)-harringtonolide has been accomplished for the first time. The key steps involved (i) a templated stereoselective IMDA reaction to build a highly functionalized cyclohexene ring D, (ii) functionalization of the cycloadduct, (iii) ring-closing metathesis providing the five-membered ring C, and finally (iv) a challenging one-step cascade cyclization of an epoxy-alcohol toward the target structure, whose mechanism was investigated

Asymmetric Synthesis of the Oxygenated Polycyclic System of (+)-Harringtonolide

A straightforward asymmetric synthesis of the cage oxygenated structure of (+)-harringtonolide has been accomplished for the first time. The key steps involved (i) a templated stereoselective IMDA reaction to build a highly functionalized cyclohexene ring D, (ii) functionalization of the cycloadduct, (iii) ring-closing metathesis providing the five-membered ring C, and finally (iv) a challenging one-step cascade cyclization of an epoxy-alcohol toward the target structure, whose mechanism was investigated

Cationic Planar Chiral (η 6 -Arene)Mn(CO) 3 + Complexes: Resolution, NMR Study in Chiral-Oriented Solvents, and Applications to the Enantioselective Synthesis of 4-Substituted Cyclohexenones and (η6 -Phosphinoarene)Mn(CO)3+ Complexes

International audienceAn easy round-trip of (D)-(þ)-camphor enolate to a racemic mixture of cationic (η6-arene)Mn-(CO)3complexes is the base of the strategy adopted for the first resolution of such complexes. X-raystructures of one of the (η5-cyclohexadienyl)Mn(CO)3 diastereoisomers obtained after addition ofthe chiral auxiliary as well as of the corresponding enantiopure η6 cationic complex after rearomatizationhave been established. Proton-decoupled deuterium 2D NMR in chiral polypeptideliquid crystals proved to be an efficient tool for the determination of the enantiomeric purity of suchplanar chiral cationic η6 complexes. The potential of this unprecedented resolution is exemplified byenantioselective syntheses in organic and organometallic fields. Thus, starting from the enantiopure(η6-meta-halogenoanisole)Mn(CO)3 complexes, enantiopure 2,4-disubstituted cyclohexenoneswere easily generated through a Mn-assisted dearomatization process, and the first examples ofenantiopure η5- and η6-phosphino-substituted Mn complexes were obtained through lithiation/electrophilic quench sequence