Synthesis, structure and dynamics of NHC-based palladium macrocycles

A series of macrocyclic CNC pincer pro-ligands based on bis(imidazolium)lutidine salts with octa-, deca- and dodecamethylene spacers have been prepared and their coordination chemistry investigated. Using a Ag2O based transmetallation strategy, cationic palladium(II) chloride complexes [PdCl{CNC–(CH2)n}][BArF4] (n = 8, 10, 12; ArF = 3,5-C6H3(CF3)2) were prepared and fully characterised in solution, by NMR spectroscopy and ESI-MS, and in the solid-state, by X-ray crystallography. The smaller macrocyclic complexes (n = 8 and 10) exhibit dynamic behaviour in solution, involving ring flipping of the alkyl spacer across the Pd–Cl bond, which was interrogated by variable temperature NMR spectroscopy. In the solid-state, distorted coordination geometries are observed with the spacer skewed to one side of the Pd–Cl bond. In contrast, a static C2 symmetric structure is observed for the dodecamethylene based macrocycle. For comparison, palladium(II) fluoride analogues [PdF{CNC–(CH2)n}][BArF4] (n = 8, 10, 12) were also prepared and their solution and solid-state structures contrasted with those of the chlorides. Notably, these complexes exhibit very low frequency 19F chemical shifts (ca. −400 ppm) and the presence of C–HF interactions (2hJFC coupling observed by 13C NMR spectroscopy). The dynamic behaviour of the fluoride complexes is largely consistent with the smaller ancillary ligand; [PdF{CNC–(CH2)8}][BArF4] exceptionally shows C2v time averaged symmetry in solution at room temperature (CD2Cl2, 500 MHz) as a consequence of dual fluxional processes of the pincer backbone and alkyl spacer

Coordination chemistry of a calix[4]arene-based NHC ligand : dinuclear complexes and comparison to IiPr2Me2

The preparation and coordination chemistry of 5,17-bis(3-methyl-1-imidazol-2-ylidene)-25,26,27,28-tetrapropoxycalix[4]arene (1) is described. Starting from the bis(imidazolium) pro-ligand 1·2HI, the free carbene 1 was readily generated in solution through deprotonation using K[OtBu] and its reactivity with rhodium(I) dimers [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) and [Rh(CO)2Cl]2 investigated. Dinuclear complexes were isolated in both cases, where the calix[4]arene-based NHC ligand adopts a bridging μ2-coordination mode, and in one case characterised in the solid-state by X-ray diffraction. Using instead an isolated and well-defined (mononuclear) silver transfer agent, generated by reaction of 1·2HI with Ag2O in the presence of a halide extractor, reactions with [Rh(COD)Cl]2 and [Rh(CO)2Cl]2 produced cationic dinuclear complexes bearing μ2-1 and μ2-Cl bridging ligands. The structural formulation of the novel dinuclear adducts of 1 was aided through spectroscopic congruence with model complexes, containing monodentate 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr2Me2)

Synthesis and reactivity of NHC-based rhodium macrocycles

Using a general synthetic procedure employing readily accessed terminal alkene-functionalized pro-ligands and macrocyclization by ring-closing olefin metathesis, rhodium carbonyl complexes have been prepared that contain lutidine (1a; n = 1) and pyridine (1b; n = 0) derived tridentate CNC macrocycles with dodecamethylene spacers. In solution, 1a shows temperature-invariant time-averaged C2 symmetry by 1H NMR spectroscopy (CD2Cl2, 500 MHz), whereas in the solid-state, two polymorphs can be obtained showing different conformations of the alkyl spacer about the metal–carbonyl bond (asymmetric and symmetric). In contrast, time-averaged motion of alkyl spacer in 1b can be halted by cooling below 225 K (CD2Cl2, 500 MHz), and the complex crystallizes as a dimer with an interesting unsupported Rh···Rh bonding interaction (3.2758(6) Å). Oxidative addition reactions of 1a and 1b, using MeI and PhICl2, have been studied in situ by 1H NMR spectroscopy, although pure Rh(III) adducts can be ultimately isolated only with the pyridine-based macrocyclic ligand. The lutidine backbone of 1a can be deprotonated by addition of K[N(SiMe3)2], and the resulting neutral dearomatized complex (5) has been fully characterized in solution, by variable-temperature 1H NMR spectroscopy, and in the solid state, by X-ray diffraction

Synthesis and complexes of imidazolinylidene-based CCC pincer ligands

A series of imidazolinium-based CCC pro-ligands featuring N-Mes, Dipp, iPr and tBu substituents (1·2HCl) have been prepared. The corresponding free carbenes are readily generated through deprotonation by strong bases and, in addition to being characterised in situ by 1H and 13C NMR spectroscopy, were trapped through reaction with CuCl. Iridium pincer compounds of the N-Mes (5a) and N-Dipp (5b) substituted ligands, viz. [Ir(1)HCl(NCMe)], were obtained through reaction between the respective pro-ligand, [Ir(COE)2Cl]2, and Et3N in acetonitrile at ca. 80 °C. Under similar conditions the N-iPr and N-tBu analogues were not formed. The new iridium pincer complexes 5a and 5b were fully characterised in solution, by NMR spectroscopy and ESI-MS, and in the solid-state by X-ray diffraction. Under relatively forcing reaction conditions neither 5a nor 5b, in combination with KOtBu, show any significant catalytic activity for the transfer dehydrogenation of cyclooctane to cyclooctene using tert-butylethylene as the sacrificial hydrogen acceptor (ca. 2 TONs, 150 °C, 24 h)

Asteroseismic surface gravity for evolved stars

Context: Asteroseismic surface gravity values can be of importance in determining spectroscopic stellar parameters. The independent log(g) value from asteroseismology can be used as a fixed value in the spectroscopic analysis to reduce uncertainties due to the fact that log(g) and effective temperature can not be determined independently from spectra. Since 2012, a combined analysis of seismically and spectroscopically derived stellar properties is ongoing for a large survey with SDSS/APOGEE and Kepler. Therefore, knowledge of any potential biases and uncertainties in asteroseismic log(g) values is now becoming important. Aims: The seismic parameter needed to derive log(g) is the frequency of maximum oscillation power (nu_max). Here, we investigate the influence of nu_max derived with different methods on the derived log(g) values. The large frequency separation between modes of the same degree and consecutive radial orders (Dnu) is often used as an additional constraint for the determination of log(g). Additionally, we checked the influence of small corrections applied to Dnu on the derived values of log(g). Methods We use methods extensively described in the literature to determine nu_max and Dnu together with seismic scaling relations and grid-based modeling to derive log(g). Results: We find that different approaches to derive oscillation parameters give results for log(g) with small, but different, biases for red-clump and red-giant-branch stars. These biases are well within the quoted uncertainties of ~0.01 dex (cgs). Corrections suggested in the literature to the Dnu scaling relation have no significant effect on log(g). However somewhat unexpectedly, method specific solar reference values induce biases of the order of the uncertainties, which is not the case when canonical solar reference values are used.Comment: 8 pages, 5 figures, accepted for publication by A&

The underlying physical meaning of the νmax−νc\nu_{\rm max}-\nu_{\rm c} relation

Asteroseismology of stars that exhibit solar-like oscillations are enjoying a growing interest with the wealth of observational results obtained with the CoRoT and Kepler missions. In this framework, scaling laws between asteroseismic quantities and stellar parameters are becoming essential tools to study a rich variety of stars. However, the physical underlying mechanisms of those scaling laws are still poorly known. Our objective is to provide a theoretical basis for the scaling between the frequency of the maximum in the power spectrum ($\nu_{\rm max}$) of solar-like oscillations and the cut-off frequency ($\nu_{\rm c}$). Using the SoHO GOLF observations together with theoretical considerations, we first confirm that the maximum of the height in oscillation power spectrum is determined by the so-called \emph{plateau} of the damping rates. The physical origin of the plateau can be traced to the destabilizing effect of the Lagrangian perturbation of entropy in the upper-most layers which becomes important when the modal period and the local thermal relaxation time-scale are comparable. Based on this analysis, we then find a linear relation between $\nu_{\rm max}$ and $\nu_{\rm c}$, with a coefficient that depends on the ratio of the Mach number of the exciting turbulence to the third power to the mixing-length parameter.Comment: 8 pages, 11 figures. Accepted in A&

Sexual and physical abuse and depressive symptoms in the UK Biobank.

BackgroundThe association between sexual and physical abuse and subsequent depression is well-established, but the associations with specific depressive symptoms and sex differences remain relatively understudied. We investigated the associations of sexual and physical abuse with depressive symptoms in men and women in a large population cohort.MethodsObservational study based on 151,396 UK Biobank participants. Exposures included self-reported experiences of childhood physical abuse and sexual abuse. Mid-life outcomes included current depressive symptoms score, individual depressive symptoms, and lifetime depression. We used logistic regression to test associations of childhood sexual/physical abuse with depressive outcomes.ResultsRecalled childhood sexual and physical abuse were both associated with current depressive symptoms score in adults. Results for individual symptoms-based analyses suggest that sexual and physical abuse are associated with all depressive symptoms, particularly suicidal behaviours. The associations between lifetime depression and sexual/physical abuse were not fully explained by current depressive symptoms score, indicating that these findings may not be fully attributable to recall bias. There was no indication of differential risk for specific depressive symptoms among men and women.ConclusionsSexual and physical abuse are robust risk factors for depression/depressive symptoms regardless of sex. Higher risk of suicidal behaviours associated with childhood sexual/physical abuse are of particular concern. Longitudinal research into sex-specific associations for individual depressive symptoms is required

Oxidative ring expansion of a low-coordinate palladacycle : synthesis of a robust T-shaped alkylpalladium(II) complex

The synthesis of an unusual T-shaped alkylpalladium(II) complex featuring a cyclometalated tri-tert-butylphosphineoxide ligand by oxidation of the corresponding cyclometalated tri-tert-butylphosphine complex with PhIO is reported. We speculate that this reaction proceeds by formation of a transient palladium oxo intermediate and there are structural similarities with a late transition metal exemplar: Milstein’s seminal pincer ligated Pt(IV) oxo (Nature 2008, 455, 1093–1096)

Sexual and physical abuse and depressive symptoms in the UK Biobank.

BackgroundThe association between sexual and physical abuse and subsequent depression is well-established, but the associations with specific depressive symptoms and sex differences remain relatively understudied. We investigated the associations of sexual and physical abuse with depressive symptoms in men and women in a large population cohort.MethodsObservational study based on 151,396 UK Biobank participants. Exposures included self-reported experiences of childhood physical abuse and sexual abuse. Mid-life outcomes included current depressive symptoms score, individual depressive symptoms, and lifetime depression. We used logistic regression to test associations of childhood sexual/physical abuse with depressive outcomes.ResultsRecalled childhood sexual and physical abuse were both associated with current depressive symptoms score in adults. Results for individual symptoms-based analyses suggest that sexual and physical abuse are associated with all depressive symptoms, particularly suicidal behaviours. The associations between lifetime depression and sexual/physical abuse were not fully explained by current depressive symptoms score, indicating that these findings may not be fully attributable to recall bias. There was no indication of differential risk for specific depressive symptoms among men and women.ConclusionsSexual and physical abuse are robust risk factors for depression/depressive symptoms regardless of sex. Higher risk of suicidal behaviours associated with childhood sexual/physical abuse are of particular concern. Longitudinal research into sex-specific associations for individual depressive symptoms is required