Controlled translocation of palladium(II) within a 22 ring atom macrocyclic ligand.

Double aza-Michael addition of n-butylamine to the two acrylamide groups of acyclic N(2),N(6)-bis(6-acrylamidopyridin-2-yl)pyridine-2,6-dicarboxamide gives the corresponding macrocycle, H4L. H4L has potential coordination pockets associated with the 2,6-dicarboxamide (head) and the butylamine (tail) regions of the macrocycle. Depending on the conditions employed, macrocyclic complexes with palladium(II) coordinated to either the tail or the head of the macrocycle can be isolated. Thus, treatment of H4L with [PdCl2(NCPh)2] and sodium acetate, or [Pd(OAc)2] gives the closely related "tail-coordinated" complexes [PdCl(H3L)] (3a) or [Pd(OAc)(H3L)] (3b), respectively. However, employment of the bases 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or pyridine during the treatment of H4L with [Pd(OAc)2] results in the "head-coordinated" complexes [Pd(NH2R)(H2L)] (NH2R = N-(3-aminopropyl)caprolactam, which is formed by hydrolysis of DBU) (5) or [Pd(OH2)(H2L)] (6), respectively. Translocation of the palladium ion from the macrocycle tail in 3b to the head occurs on treatment with either DBU or N-(3-aminopropyl)caprolactam. In both cases the product 5 is formed. The aqua ligand in 6 is labile and easily displaced by the N-donor ligands n-butylamine, N-(3-aminopropyl)caprolactam or DBU to give the corresponding complexes [Pd(NH2(n)Bu)(H2L)] (4), (5), or [Pd(DBU)(H2L)] (7). The data suggest that hydrolysis of DBU to produce the N-(3-aminopropyl)caprolactam ligand in 5 is catalysed by the acetic acid formed during ligand metallation rather than by coordination to palladium. The X-ray crystal structures of H4L, 5, and 6 are reported.

Validation of the joint commission exclusion criteria for elective early-term delivery.

OBJECTIVE: To evaluate whether current Joint Commission (JC) exclusion criteria for measure PC-01, "Elective Delivery" before 39 weeks of gestation, accurately identify valid, codeable indications for planned early-term delivery. METHODS: We performed a review and critical analysis of all cases recorded as noncompliant for the measure in a large health care system during the second half of 2012. RESULTS: During the study period, of 107,145 total deliveries, 205 cases were reported as noncompliant with PC-01. Ten percent of compliance fallouts (ie, cases coded as noncompliant) resulted from valid indications for delivery identifiable by International Classification of Diseases, 9th Revision, Clinical Modification (ICD-9-CM) coding not included on the JC exclusion list; these were primarily unusual or extreme variations of these conditions. Twenty-five percent of fallouts represented valid indications not represented by an ICD-9-CM code. Eight percent of cases were reported as fallouts as a result of imprecise physician charting; only 2% represented chart abstraction errors. Fifty-five percent of cases involved stated indications for early-term delivery not generally recognized as such by the medical community. Compliance rates of 98% are achievable across a large population using the current ICD-9-CM-based metric for compliance assessment used by the JC (PC-01). The current exclusion list does not appear to be amenable to further improvement by inclusion of more or different ICD-9-CM codes. However, given the low volumes generated using the current PC-01 denominator definition, approximately 60% of facilities would have compliance rates below a 95% benchmark with even a single justified outlier if analyzed on a quarterly basis. CONCLUSION: Our data validate the current JC exclusion criteria for this measure, which identify the vast majority of valid indications for early-term delivery used by obstetrician-gynecologists and identifiable with ICD-9-CM codes. LEVEL OF EVIDENCE: III.

Rapid core measure improvement through a "business case for quality".

Incentives to improve performance are emerging as revenue or financial penalties are linked to the measured quality of service provided. The HCA "Getting to Green" program was designed to rapidly increase core measure performance scores. Program components included (1) the "business case for quality"-increased awareness of how quality drives financial performance; (2) continuous communication of clinical and financial performance data; and (3) evidence-based clinical protocols, incentives, and tools for process improvement. Improvement was measured by comparing systemwide rates of adherence to national quality measures for heart failure (HF), acute myocardial infarction (AMI), pneumonia (PN), and surgical care (SCIP) to rates from all facilities reporting to the Centers for Medicare and Medicaid Services (CMS). As of the second quarter of 2011, 70% of HCA total measure set composite scores were at or above the 90th percentile of CMS scores. A test of differences in regression coefficients between the CMS national average and the HCA average revealed significant differences for AMI (p = .001), HF (p = .012), PN (p < .001), and SCIP (p = .015). This program demonstrated that presentation of the financial implications of quality, transparency in performance data, and clearly defined goals could cultivate the desire to use improvement tools and resources to raise performance.

Synthesis and structure of K+ [iPrN=C=P]-, a 1-aza-3lambda3-phospha-3-allenide.

2-Isopropyl(trimethylsilyl)amino-1lambda3-phosphaalkyne 1 reacts with potassium tert-butoxide to form potassium 1-isopropyl-1-aza-3lambda3-phospha-3-allenide (2). This compound was structurally characterized as the corresponding 18-crown-6 ether complex 3. The molecular structure of 1 was also determined in order to compare the bonding situation in the anion and the neutral lambda3-phosphaalkyne. Compound 3 contains a nitrogen-carbon-phosphorus group for which the parameters were shown by X-ray structural analysis and quantum chemical calculations to lie between the extrema N-C[triple bond]P and N=C=P, suggesting reactivity typical of an ambident anion. This is indeed the case, as subsequent reaction of 2 with chlorotrimethylsilane at nitrogen regenerates the lambda3-phosphaalkyne 1; with chlorotriphenylsilane the new derivative 4 is formed. In contrast, chlorotrimethylstannane reacts at phosphorus, giving the 1-aza-3lambda3-phosphaallene isopropyliminomethylidene(trimethylstannyl)phosphane 5.

Luminescent gold(I) and silver(I) complexes of 2-(diphenylphosphino)-1-methylimidazole (dpim): characterization of a three-coordinate Au(I)-Ag(I) dimer with a short metal-metal separation.

The Au(I) and Ag(I) closed-shell metal dimers of 2-(diphenylphosphino)-1-methylimidazole, dpim, were investigated. dpim formed the discreet binuclear species [Ag2(dpim)2(CH3CN)2](2+) (1) when reacted with appropriate Ag(I) salts. Likewise, [Au2(dpim)2](2+) (3) and [AuAg(dpim)3](2+) (4) were produced via reactions with (tht)AuCl, tht is tetrahydrothiophene, and Ag(I). Compound 3 exhibits an intense blue luminescence (lambdamax=483 nm) in the solid state. However, upon initial formation of 3, a small impurity of Cl- was present giving rise to an orange emission (lambdamax=548 nm). Attempts to form [Au2(dpim)2]Cl2 yielded only (dpim)AuCl (2), which is not visibly emissive. The rare three-coordinate heterobimetallic complex [AuAg(dpim)3](2+) (4) exhibits intense luminescence in the solid-state resembling that of 3. The crystal structures of 1-4 were determined, revealing strong intramolecular aurophilic and argentophilic interactions in the dimeric compounds. Compound 1 has an Ag(I)-Ag(I) separation of 2.9932(9) A, while compound 3 has a Au(I)-Au(I) separation of 2.8174(10) A. Compound 4 represents the first example of a three-coordinate Au(I)-Ag(I) dimer and has a metal-metal separation of 2.8635(15) A. The linear Au(I) monomer, 2, has no intermolecular Au(I)-Au(I) interactions, with the closest separation greater than 6.8 A.

Three- and four-coordinate gold(I) complexes of 3,6-bis(diphenylphosphino)pyridazine: monomers, polymers, and a metallocryptand cage.

The slightly yellow polymeric complexes [Au(2)Cl(2)(P(2)pz)(3)](n), 1 x 6CHCl(3), (P(2)pz is 3,6-bis(diphenylphosphino)pyridazine) and [[Au(2)(P(2)pz)(3)](PF(6))(2)](n), 2, are prepared by the stoichiometric reaction of AuCl(tht) (tht is tetrahydrothiophene) and P(2)pz in either dichloromethane or dichloromethane/methanol, respectively. Addition of 2 equiv of AuCl(tht) to a dichloromethane solution of 1 equiv of P(2)pz generates the simple (AuCl)(2)(P(2)pz) compound, 3. Compound 3 contains nearly linear P-Au-Cl units with intermolecular Au.Au separations of 3.570 A. Au(2)I(2)(P(2)pz)(3), 4, is prepared by reacting excess NaI with 2 in a dichloromethane/methanol mixture. Characterization of 1, 2, and 4 by X-ray crystallography confirms the 2:3 gold/ligand ratio of all three complexes. The coordination polymer 1 maintains a high degree of solvation in the solid-state with three chloroform adducts hydrogen-bonded to the chloride ligand on each gold atom. These chloroform molecules are sandwiched between the two-dimensional polymeric sheets of 1. The crystal structure of 4 reveals an empty, iodide-capped metallocryptand cage with the tetrahedrally distorted gold atoms and the nitrogen atoms on the pyridazine rings directed away from the center of the cavity. No metal ion encapsulation was observed for complex 4. Complex 2 forms one-dimensional arrays of [Au(2)(P(2)pz)(2)](2+) metallomacrocycles connected to each other by a third P(2)pz ligand. The electronic absorption spectra (CH(2)Cl(2)) of 1-4 show broad, nearly featureless absorption bands that tail into the visible with pi-pi bands at 296 nm and discernible shoulders at 314 nm for 2 and 334 nm for 3. Excitation into the low energy band of 2 produces only a modest emission in solution at 540 nm (lambda(ex) 468 nm) and 493 nm (lambda(ex) 403 nm). Under identical conditions, the P(2)pz ligand also emits at 540 and 493 nm.