18 research outputs found
Neutralising antibodies after COVID-19 vaccination in UK haemodialysis patients
Vaccination against COVID-19 induces highly protective immune responses in most people. As some countries switch from suppression to acceptance of transmission of SARS-CoV-2 within a largely vaccinated adult population, vulnerable patient groups that have not mounted adequate immune responses to vaccination might experience significant morbidity and mortality. There is an urgent need to identify such patient groups and to optimise medical advice and vaccination strategies for them
Use of ring-expanded diamino- and diamidocarbene ligands in copper catalyzed azide-alkyne "click" reactions
The
two-coordinate ring-expanded N-heterocyclic carbene copperÂ(I)
complexes [CuÂ(RE-NHC)<sub>2</sub>]<sup>+</sup> (RE-NHC = 6-Mes, 7-<i>o</i>-Tol, 7-Mes) have been prepared and shown to be effective
catalysts under neat conditions for the 1,3-dipolar cycloaddition
of alkynes and azides. In contrast, the cationic diamidocarbene analogue
[CuÂ(6-MesDAC)<sub>2</sub>]<sup>+</sup> and the neutral species [(6-MesDAC)ÂCuCl]<sub>2</sub> and [(6-MesDAC)<sub>2</sub>(CuCl)<sub>3</sub>] show good
activity when the catalysis is performed on water
Mechanistic Studies of the Rhodium NHC Catalyzed Hydrodefluorination of Polyfluorotoluenes
The six-membered-ring NHC complexes
RhÂ(6-NHC)Â(PPh<sub>3</sub>)<sub>2</sub>H (6-NHC <b>=</b> 6-<sup>i</sup>Pr (<b>1</b>),
6-Et (<b>2</b>), 6-Me (<b>3</b>)) have been employed in
the catalytic hydrodefluorination (HDF) of C<sub>6</sub>F<sub>5</sub>CF<sub>3</sub> and 2-C<sub>6</sub>F<sub>4</sub>HCF<sub>3</sub>. Stoichiometric
studies showed that <b>1</b> reacted with C<sub>6</sub>F<sub>5</sub>CF<sub>3</sub> at room temperature to afford <i>cis</i>- and <i>trans</i>-phosphine isomers of RhÂ(6-<sup>i</sup>Pr)Â(PPh<sub>3</sub>)<sub>2</sub>F (<b>4</b>), which re-form <b>1</b> upon heating with Et<sub>3</sub>SiH. Although up to three
consecutive HDF steps prove possible with C<sub>6</sub>F<sub>5</sub>CF<sub>3</sub>, the ultimate effectiveness of the catalysts is limited
by their propensity to undergo CâH activation of partially
fluorinated toluenes to give, for example, RhÂ(6-<sup>i</sup>Pr)Â(PPh<sub>3</sub>)<sub>2</sub>(C<sub>6</sub>F<sub>4</sub>CF<sub>3</sub>) (<b>7</b>), which was isolated and structurally characterized
Copper Diamidocarbene Complexes: Characterization of Monomeric to Tetrameric Species
Treatment of CuCl with 1 equiv of
the in situ prepared <i>N</i>-mesityl-substituted diamidocarbene
6-MesDAC produced a mixture of the dimeric and trimeric copper complexes
[(6-MesDAC)ÂCuCl]<sub>2</sub> (<b>1</b>) and [(6-MesDAC)<sub>2</sub>(CuCl)<sub>3</sub>] (<b>2</b>). Combining CuCl with
isolated, free 6-MesDAC in 1:1 and 3:2 ratios gave just <b>1</b> and <b>2</b>, respectively, while increasing the ratio to
>5:1 allowed the isolation of small amounts of the tetrameric copper
complex [(6-MesDAC)<sub>2</sub>(CuCl)<sub>4</sub>] (<b>3</b>). Efforts to bring about metathesis reactions of <b>1</b> with
MO<sup>t</sup>Bu (M = Li, Na, K) proved successful only for M = Li
to afford the spectroscopically characterized ate product [(6-MesDAC)ÂCuCl·LiO<sup>t</sup>Bu·2THF] (<b>5</b>). Attempts to crystallize this
species instead gave a 1:1 mixture of <b>1</b> and the monomer
[(6-MesDAC)ÂCuCl] (<b>6</b>). The X-ray structures of <b>1</b>â<b>3</b> and <b>1</b> + <b>6</b>, along
with the cation [CuÂ(6-MesDAC)<sub>2</sub>]<sup>+</sup> (<b>4</b>), have been determined
Slow Magnetic Relaxation in Octahedral Cobalt(II) Field-Induced Single-Ion Magnet with Positive Axial and Large Rhombic Anisotropy
Stereoelectronic Effects in CâH Bond Oxidation Reactions of Ni(I) N-Heterocyclic Carbene Complexes
Mesoionic triazolylidene nickel complexes: synthesis, ligand lability, and catalytic CâC bond formation activity
A set of triazolylidene (trz) nickel(II) complexes [NiCpX(trz)] was synthesized by a direct metalation of the corresponding triazolium salt with nickelocene, NiCp2. While at short reaction times and in the presence of a coordinating anion X the mono-carbene complex is preferably formed, long reaction times induce the gradual transformation of [NiCpX(trz)] to the bis-carbene complexes [Ni(Cp)(trz)2]+. Kinetic analyses lend strong support to a consecutive pathway involving triazolylidene dissociation from [NiCpX(trz)] en route to the bis-carbene complex. Similar carbene transfer is observed in a solid-state reaction upon heating the complex [NiCpI(trz)] in vacuo, which induces disproportionation to [NiI2(trz)2] and NiCp2, confirming that the NiâC(trz) bond is kinetically labile. The complexes [Ni(Cp)(trz)2]+ and [NiCpX(trz)] were both efficient catalyst precursors for SuzukiâMiyaura cross-coupling of aryl bromides and phenylboronic acid, with turnover frequencies exceeding 228 hâ1. Complex degradation after short reaction times, identified in separate experiments, prohibits high turnover numbers, and for high conversions, repetitive additions of triazolylidene nickel complex and phenylboronic acid are necessary.European Research Counci