The anions [(ZrOH(CO3)3)2]6− and [(ZrOH(C2O4)3)2]6−: single crystal X-ray diffraction studies of the complexes guanidinium zirconium carbonate [(C(NH2)3)3ZrOH(CO3)3·H2O]2 and sodium zirconium oxalate Na6(ZrOH(C2O4)3)2·7H2O

The complex [(C(NH2)3)3ZrOH(CO3)3·H2O]2 (A) has been shown by means of a single crystal X-ray diffraction study to contain [C(NH2)3]+ cations and dimeric anions of formulation [(ZrOH(CO3)3)2]6−. The anion is centrosymmetric with each metal being bonded to two bridging OH groups and three chelating CO2−3 ions. The Zr atoms are thus eight coordinate with a dodecahedral environments. The ZrO distances formed by the bridgng OH groups are shorter than those formed through zirconiu carbonate interactions. The non-bonded Zr…Zr distance is 3.47(2) Å. An infrared spectroscopic investigation of A provides data which support the findings of the crystallographic study. Likewise the complex Na6(ZrOH(CO2O4)3)2·7H2O (B) contains the anion [(ZrOH(C2O4)3)2]6−. This anion is structurally related to the anion in A as each Zr atom has an eight-coordinate dodecahedral environment being bonded to two bridging OH groups and three chelating oxalate ligands, but has no imposed crysallographic symmetry. The Zr…Zr non-bonded distance is 3.50(1) Å. The OZrO bridge angles are 69.7(4)° and A and 67.4(3)° in B.

Metal complexes with atropisomeric sulfur ligands in asymmetric hydroformylation X-ray structure of [Rh2(μ-biphes)(cod)2] (H2biphes = 4,4′-biphenanthrene-3,3′-dithiol)

The addition of the atropisomeric racemic sulfur compound 4,4′-biphenanthrene-3,3′-dithiol (H2 biphes) to a dichloromethane solution of [{M(μ-OMe)(cod)}2] (M = Rh, Ir, cod = cycloocta-1,5-diene) afforded the dithiolate-bridged complexes [{Rh2(μ-biphes)(cod)2}n] (n = 2 5 or n = 1 6) and [{Ir2(μ-biphes)(cod)2}n]·nCH2Cl27. When 1,1′-binaphthalene-2,2′-dithiol (H2 binas) reacted with [{Ir(μ-OMe)(cod)}2], complex [Ir2(μ-binas)(cod)2] 8 was obtained. Complexes 5 and 6 reacted with carbon monoxide to give the dinuclear tetracarbonyl complex [Rh2(μ-biphes)(CO)4] 9. The reaction of 9 with PR3 provided the mixed-ligand complexes [{Rh2(μ-biphes)(CO)2(PR3)2}2] · xCH2Cl2 (R = Ph, x = 2 10, C6H11, x = 1 11) and [{Rh2(μ-biphes)(CO)3(PR3)}2] · CH2Cl212 (R = OC6H4But-o). The crystal structure of 6 was determined by X-ray diffraction. Reaction of the dithioether ligand Me2biphes with [Rh(cod)2]ClO4 in CH2Cl2 solution afforded the cationic complex [Rh(cod)(Me2biphes)]ClO4 · CH2Cl213. Asymmetric hydroformylation of styrene was performed using the complexes described. The extent of aldehyde conversion ranges from 53 to 100%, with selectivities towards branched aldehydes in the range 51 to 96%. The enantioselectivities were quite low and did not exceed 20%.

Synthesis and reactions of [Et3NH]4[Mo8O6]: X-ray crystal structure of [Et3NH]3[NaMo8O26]

[Et3NH]4[Mo8O26] (1) was prepared by reacting triethylamine with either molybdenum trioxide dihydrate or with a solution of ammonium molybdate in aqueous HCl. An aqueous solution of complex 1 reacted with an excess of sodium chloride to give a mixture of [Et3NH]3[NaMo8O26] (2) and [Et3NH]2[Mo6O19] (3). Complex 2 was also formed on reacting sodium molybdate with triethylamine in aqueous HCl. In the reaction of 1 with potassium chloride the nature of the product obtained was critically dependent upon reaction time. After a 5.5 h reflux period a mixture of [Et3NH]3[KMo8O26] (4) and 3 was obtained, whereas upon prolonged reflux (24 h) only K4Mo8O26 · H2O (5) was precipitated. The X-ray crystal structure of 2 shows it to be polymeric, with each Na+ ion sandwiched between two β[Mo8O26]4− ions. Four oxygen atoms on one face of each β[Mo8O26]4− ion are coordinated to a Na+ ion, and four oxygens from the opposite face are bonded to the next Na+ ion in the polymer chain. This produces a zig-zag arrangement of Na+ ions throughout the molecular structure. Spectral, conductivity and voltammetry data are given.

Extending the Lincoln–Petersen estimator for multiple identifications in one source

The Lincoln–Petersen estimator is one of the most popular estimators used in capture–recapture studies. It was developed for a sampling situation in which two sources independently identify members of a target population. For each of the two sources, it is determined if a unit of the target population is identified or not. This leads to a 2 × 2 table with frequencies f11, f10, f01, f00 indicating the number of units identified by both sources, by the first but not the second source, by the second but not the first source and not identified by any of the two sources, respectively. However, f00 is unobserved so that the 2 × 2 table is incomplete and the Lincoln–Petersen estimator provides an estimate for f00. In this paper, we consider a generalization of this situation for which one source provides not only a binary identification outcome but also a count outcome of how many times a unit has been identified. Using a truncated Poisson count model, truncating multiple identifications larger than two, we propose a maximum likelihood estimator of the Poisson parameter and, ultimately, of the population size. This estimator shows benefits, in comparison with Lincoln–Petersen’s, in terms of bias and efficiency. It is possible to test the homogeneity assumption that is not testable in the Lincoln–Petersen framework. The approach is applied to surveillance data on syphilis from Izmir, Turkey.

Spectroelectrochemical study of complexes [Mo(CO)2(h3-allyl)(adiimine)(NCS)] (a-diimine ¼ bis(2,6-dimethylphenyl)- acenaphthenequinonediimine and 2,20-bipyridine) exhibiting different molecular structure and redox reactivity

The redox properties and reactivity of [Mo(CO)2(η3-allyl)(α-diimine)(NCS)] (α-diimine = bis(2,6-dimethylphenyl)-acenaphthenequinonediimine (2,6-xylyl-BIAN) and 2,2′-bipyridine (bpy)) were studied using cyclic voltammetry and IR/UV–Vis spectroelectrochemistry. [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN)(NCS)] was shown by X-ray crystallography to have an asymmetric (B-type) conformation. The extended aromatic system of the strong π-acceptor 2,6-xylyl-BIAN ligand stabilises the primary 1e−-reduced radical anion, [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN•−)(NCS)]−, that can be reduced further to give the solvento anion [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN)(THF)]−. The initial reduction of [Mo(CO)2(η3-allyl)(bpy)(NCS)] in THF at ambient temperature results in the formation of [Mo(CO)2(η3-allyl)(bpy)]2 by reaction of the remaining parent complex with [Mo(CO)2(η3-allyl)(bpy)]− produced by dissociation of NCS− from [Mo(CO)2(η3-allyl)(bpy•−)(NCS)]−. Further reduction of the dimer [Mo(CO)2(η3-allyl)(bpy)]2 restores [Mo(CO)2(η3-allyl)(bpy)]−. In PrCN at 183 K, [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN•−)(NCS)]− converts slowly to 2e−-reduced [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN)(PrCN)]− and free NCS−. At room temperature, the reduction path in PrCN involves mainly the dimer [Mo(CO)2(η3-allyl)(bpy)]2; however, the detailed course of the reduction within the spectroelectrochemical cell is complicated and involves a mixture of several unassigned products. Finally, it has been shown that the five-coordinate anion [Mo(CO)2(η3-allyl)(bpy)]− promotes in THF reduction of CO2 to CO and formate via the formation of the intermediate [Mo(CO)2(η3-allyl)(bpy)(O2CH)] and its subsequent reduction.

A novel ensemble method for retrieving properties of warm cloud in 3-D using ground-based scanning radar and zenith radiances

We present a novel method for retrieving high-resolution, three-dimensional (3-D) nonprecipitating cloud fields in both overcast and broken-cloud situations. The method uses scanning cloud radar and multiwavelength zenith radiances to obtain gridded 3-D liquid water content (LWC) and effective radius (re) and 2-D column mean droplet number concentration (Nd). By using an adaption of the ensemble Kalman filter, radiances are used to constrain the optical properties of the clouds using a forward model that employs full 3-D radiative transfer while also providing full error statistics given the uncertainty in the observations. To evaluate the new method, we first perform retrievals using synthetic measurements from a challenging cumulus cloud field produced by a large-eddy simulation snapshot. Uncertainty due to measurement error in overhead clouds is estimated at 20% in LWC and 6% in re, but the true error can be greater due to uncertainties in the assumed droplet size distribution and radiative transfer. Over the entire domain, LWC and re are retrieved with average error 0.05–0.08 g m-3 and ~2 μm, respectively, depending on the number of radiance channels used. The method is then evaluated using real data from the Atmospheric Radiation Measurement program Mobile Facility at the Azores. Two case studies are considered, one stratocumulus and one cumulus. Where available, the liquid water path retrieved directly above the observation site was found to be in good agreement with independent values obtained from microwave radiometer measurements, with an error of 20 g m-2.

Recognition, assessment and treatment of social anxiety disorder: summary of NICE guidance

Social anxiety disorder is one of the most persistent and common of the anxiety disorders, with lifetime prevalence rates in Europe of 6.7% (range 3.9-13.7%).1 It often coexists with depression, substance use disorder, generalised anxiety disorder, panic disorder, and post-traumatic stress disorder.2 It can severely impair a person’s daily functioning by impeding the formation of relationships, reducing quality of life, and negatively affecting performance at work or school. Despite this, and the fact that effective treatments exist, only about half of people with this condition seek treatment, many after waiting 10-15 years.3 Although about 40% of those who develop the condition in childhood or adolescence recover before adulthood,4 for many the disorder persists into adulthood, with the chance of spontaneous recovery then limited compared with other mental health problems. This article summarises the most recent recommendations from the National Institute for Health and Care Excellence (NICE) on recognising, assessing, and treating social anxiety disorder in children, young people, and adults.5