Dinitrogen functionalization at a ditantalum center. Balancing N displacement and N functionalization in the reaction of coordinated N with CS.

The reaction of carbon disulfide (CS2) with the side-on end-on dinitrogen complex ([NPNSi]Ta)2(μ-η1:η2-N2)(μ-H)2 (1) (where [NPNSi] = [PhP(CH2SiMe2NPh)2]) has been studied and shown to generate two products, the ratio of which depends on the concentration of added carbon disulfide. At high concentrations of CS2, N-N bond cleavage and functionalization occur to generate a ditantalum complex with an isothiocyanato ligand N-bound to Ta along with bridging sulfido and nitrido moieties. At lower concentrations of CS2, less dinitrogen functionalization is observed; instead, N2 is displaced and the CS2 molecule is completely disassembled to generate a ditantalum derivative with bridging methylene and two sulfide moieties.

Cationic mono and dicarbonyl pincer complexes of rhodium and iridium to assess the donor properties of PCcarbeneP ligands.

The donor properties of five different PCcarbeneP ligands are assessed by evaluation of the CO stretching frequencies in iridium(i) and rhodium(i) carbonyl cations. The ligands feature dialkyl phosphine units (R = (i)Pr or (t)Bu) linked to the central benzylic carbon by either an ortho-phenylene bridge, or a 2,3-benzo[b]thiophene linker; in the former, substituent patterns on the phenyl linker are varied. The carbonyl complexes are synthesized from the (PCcarbeneP)M-Cl starting materials via abstraction of the chlorides in the presence of CO gas.

Diels-Alder Reactions of 1,2-Azaborines.

Diels-Alder reactions employing 1,2-azaborine heterocycles as 1,3-dienes are reported. Carbocyclic compounds with high stereochemical and functional complexity are produced, as exemplified by the straightforward two-step synthesis of an amino allyl boronic ester bearing four contiguous stereocenters as a single diastereomer. Whereas electron-deficient dienophiles undergo irreversible Diels-Alder reactions, a reversible Diels-Alder reaction with the less electron-deficient methyl acrylate is observed.

Reversible interconversion between a monomeric iridium hydroxo and a dinuclear iridium μ-oxo complex.

Treatment of the (PCsp(2)P)Ir(I)Cl complexes 2(R) (R = (i)Pr, (t)Bu) with cesium hydroxide in THF leads to the corresponding monomeric Ir(I) hydroxo complexes 5(R) in good to excellent yields of 70% (R = (i)Pr) and 92% (R = (t)Bu). The compounds are green in color and while they exhibit very similar (31)P NMR data to the chlorides 2, the (1)H NMR spectrum of each features a triplet ((3)JHP = 3.8 Hz) at 4.

Pay for performance: an excellent idea that simply needs implementation.

Pay for performance cannot consist of a one-size-fits-all approach. Variation in quality and cost of care is best measured using a single "value" (quality/cost) score that is decomposed into component cost and quality for every health care encounter type. Economic incentives must be enough to focus the provider's attention on each score part.