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Before you take off for the landing zone, make sure you know what you and your colleagues need to do to stay safe and protect the patient during transfer. Use these photos as a guide. [ABSTRACT FROM AUTHOR]

Background: Many inpatients experience cardiac arrest and mortality in this population is extremely high. Simulation is frequently used to train code teams with the goal of improving these outcomes. A key step in designing such a training curriculum is to perform a needs assessment. We report on the effectiveness of a simulation-based training program for residents designed using unannounced in-situ simulation cardiac arrest data as a needs assessment., Methods: In order to develop the curriculum for training, a needs assessment was done using in-situ simulation. Prior to instruction, residents were assessed in their ability to lead a simulated resuscitation using a standardized checklist. During the intervention phase, residents participated in didactic and team training. The didactic training consisted of pharmacology review, ACLS update and TeamSTEPPS training. Residents took turns as code team leader in three simulation sessions. Rapid cycle deliberate practice (RCDP) was employed as part of simulation sessions. All residents returned, for post-intervention assessment. Mean pre-post test scores were analyzed to determine if there was a significant difference., Results: Twenty-seven residents participated. Mean pre-training assessment score was 47.6 (95% CI 37.5-57.9). The mean post-training assessment score was 84.4 (95% CI 79.0-89.5). The mean time to defibrillation after pads were placed in scenario with shockable rhythm decreased from 102.2 seconds (95% CI 74.0-130.5) to 56.3 (95% CI 32.7-79.8)., Conclusion: Using unannounced in-situ cardiac arrest simulations as a needs assessment, a simulation-based training program was developed that significantly improved resident performance as team leader. Future work is needed to determine if this improvement translates into patient benefits and is sustainable. However, in-situ simulation is a promising tool for curriculum development., Competing Interests: Competing interestsThe authors declare that they have no competing interests., (© The Author(s) 2020.)

The crystal structures of two crystalline phases of 1,4-di-thiane 1,1,4,4-tetra-oxide, C 4 H 8 O 4 S 2 , have been determined in order to examine the nature of possible inter-molecular hydrogen bonds. Phase 1 is monoclinic, space group C 2/ m , with unit-cell dimensions of a = 9.073 (8), b = 7.077 (6), c = 5.597 (5) Å and β = 105.89 (1)°. The mol-ecule adopts 2/ m symmetry and all of the mol-ecules are related by translation and thus have the same orientation. Phase 2 is also monoclinic but in space group P 2 1 / n with unit-cell dimensions of a = 7.1305 (5), b = 5.7245 (4), c = 8.3760 (6) Å and β = 91.138 (2)°. In this phase, the mol-ecule sits on an inversion center and the mol-ecules within the unit cell adopt quite different orientations. In both phases, examination of the potential C-H⋯O hydrogen bonds around each of the independent oxygen atoms (one axial and the other equatorial) shows the general O⋯H patterns to be quite similar with each oxygen atom in contact with four neighboring H atoms, and each H atom contacting two neighboring O atoms. While none of the H⋯O contacts is particularly short (all are greater than 2.5 Å), each mol-ecule has 32 such contacts that form an extensive inter-molecular network. A 1 H NMR spectrum of the compound dissolved in DMSO shows a singlet of 8H at δ 3.677 which indicates that the C-H bonds are only moderately polarized by the single adjacent -SO 2 - moiety: strongly polarized C-H bonds have δ values in the 5-6 range [Li & Sammes (1983 ▸). J. Chem. Soc. Perkin Trans. 1 , pp. 1303-1309]. The phase 1 crystal studied was non-merohedrally twinned.

Cortical activity is maintained by neural networks working in tandem. Electroencephalographic (EEG) signals across two sites are said to be coherent with one another when they show consistent phase relations. However, periods of desynchrony beginning with a shift in phase relations are a necessary aspect of information processing. Traditional measures of EEG coherence lack the temporal resolution required to divide the relationship between two signals into periods of synchrony and desynchrony and are unable to specify the direction of information transmission (i.e., which site is leading and which is lagging), a goal referred to as directed connectivity. In this article, the authors introduce a novel method of measuring directed connectivity by applying the framework of Granger causality to phase shift events which are estimated with high temporal resolution. A simulation study is used to verify that the proposed method is able to identify connectivity patterns in situations similar to EEG recordings, such as high levels of noise and linear source mixing. Their method is able to correctly identify both the existence and direction of information transfer, and that the existence of spatiotemporal noise serves to reduce the spread of shift identification due to volume conduction. To demonstrate the method on real data, it is applied to EEG recordings from 18 adolescents during a resting period and auditory and visual vigilance tasks. Their new measure, Phase Shift Granger Causality (PSGC), is able to clearly distinguish between the resting task and the active tasks. The latter have higher rates of connectivity overall and specifically more long-range connections. As expected, the resting task appears to activate more localized neural circuitry, whereas the active tasks appear to increase communication across several neural regions involved in vigilance tasks. The vigilance tasks also showed significantly higher clustering coefficients than the resting task, a property associated with small-world networks.

Increasing evidence supports the notion that both internalizing (e.g., anxiety) and externalizing (e.g., aggression) behavioral dysregulation are associated with abnormal communication between brain regions. Electroencephalographic (EEG) signals across two electrode sites are said to be coherent with one another when they show consistent phase relations. However, periods of desynchrony with shifting of phase relations are a necessary aspect of information processing. The components of EEG phase reset ('locking' when two regions remain in synchrony, and 'shifting' when the two regions desynchronize momentarily) show dramatic changes across development. We collected resting EEG data from typically developing 12 to 15-year-olds and calculated phase shift and lock values in the alpha frequency band across 14 pairs of electrodes varying in inter-electrode distance. A composite measure of participants' aggression levels was positively associated with phase shifting, particularly in the low alpha frequency range, most strongly over the left hemisphere, consistent with the relatively greater left-prefrontal activity reported in aggressive adults. A composite measure of anxiety levels was positively associated with alpha phase locking at sites over both hemispheres, consistent with changes in connectivity reported during anxious thinking in adults. Associations with anxiety could not be explained by traditional EEG coherence measures and suggest that phase shifting and locking might provide an important non-invasive associate of clinically problematic behavior., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Background and Purpose: Few studies have explored optimal advancement and variation in mobility and length of stay (LOS) data with critically ill patients in the intensive care unit (ICU). The purpose of this study was to analyze the outcomes and LOS of critically ill patients in the neurotrauma ICU involved in rehabilitation., Methods: A bidirectional case-control study of a total of 30 patients admitted to a level 1 trauma hospital in the metropolitan Chicago area with Glasgow Coma Score (GCS) of ≤12 (3-12) were studied. Functional outcomes of a structured mobility group were compared at first upright sitting and at ICU discharge using the functional independence measure (FIM). Retrospective LOS review of a group (n = 15) with unstructured activity advancement was compared., Results: The main outcome measures were FIM scores and LOS in number of days. In the structured mobility group, a significant increase in functional performance between first upright sitting and ICU discharge was found (P < .005). Length of stay was shorter in the structured mobility groups but the difference was not statistically significant., Conclusions: Results from this study revealed favorable functional outcomes for patients involved in a structured mobility program with physical therapy in the neuro/trauma ICU.

NMR studies of intramolecular exchange in [(Ph(3)P)(3)Rh(X)] (X = CF(3), CH(3), H, Ph, Cl) have produced full sets of activation parameters for X = CH(3) (E(a) = 16.4 +/- 0.6 kcal mol(-1), DeltaH(double dagger) = 16.0 +/- 0.6 kcal mol(-1), and DeltaS(double dagger) = 12.7 +/- 2.5 eu), H (E(a) = 10.7 +/- 0.2 kcal mol(-1), DeltaH(double dagger) = 10.3 +/- 0.2 kcal mol(-1), and DeltaS(double dagger) = -7.2 +/- 0.8 eu), and Cl (E(a) = 16.3 +/- 0.2 kcal mol(-1), DeltaH(double dagger) = 15.7 +/- 0.2 kcal mol(-1), and DeltaS(double dagger) = -0.8 +/- 0.8 eu). Computational studies have shown that for strong trans influence ligands (X = H, Me, Ph, CF(3)), the rearrangement occurs via a near-trigonal transition state that is made more accessible by bulkier ligands and strongly donating X. The exceedingly fast exchange in novel [(Ph(3)P)(3)Rh(CF(3))] (12.1 s(-1) at -100 degrees C) is due to strong electron donation from the CF(3) ligand to Rh, as demonstrated by computed charge distributions. For weaker donors X, this transition state is insufficiently stabilized, and hence intramolecular exchange in [(Ph(3)P)(3)Rh(Cl)] proceeds via a different, spin-crossover mechanism involving triplet, distorted-tetrahedral [(Ph(3)P)(3)Rh(Cl)] as an intermediate. Simultaneous intermolecular exchange of [(Ph(3)P)(3)Rh(Cl)] with free PPh(3) (THF) via a dissociative mechanism occurs exclusively from the sites cis to Cl (E(a) = 19.0 +/- 0.3 kcal mol(-1), DeltaH(double dagger) = 18.5 +/- 0.3 kcal mol(-1), and DeltaS(double dagger) = 4.4 +/- 0.9 eu). Similar exchange processes are much slower for [(Ph(3)P)(3)Ir(Cl)] which has been found to exist in orange and red crystallographic forms isostructural with those of [(Ph(3)P)(3)Rh(Cl)].

Novel rearrangements of 2,3,2',3'-tetra-tert-butyl-4,4'-bis-trimethylsilanyloxy-1,2,1',2'-tetrahydro-[1,1']biphosphetyl (7) to 1,2,5,6-tetra-tert-butyl-3,7-bis-trimethylsilanyloxy-1H,5H-[1,2]diphospholo-[1,2-a][1,2]diphosphole (9) and of 3,4,3,4-tetra-tert-butyl-[1,1']biphosphetanyl-2,2'-dione (10) to 2,3,6,7-tetra-tert-butyl-tetrahydro-[1,2]diphospholo[1,2-a][1,2]diphosphole-1,5-dione (12) were observed during sublimation at 150 degrees C in 0.1 mm vacuum. The C-P-C internal angles of the four-membered rings, which reflect steric strain in (7), were 71.9(2) degrees and 77.9(1) degrees; the C-P-P internal angles of the five-membered rings of 9 were 90.88(6) degrees and 93.02(6) degrees after rearrangement. Reaction of 7 with metallic caesium provided the caesium salt of 3,4-di-tert-butyl-3,4-dihydro-phosphet-2-ol (15), which is the first example of a 2lambda-3-phospha-1-enolate being incorporated into four-membered ring. Due to its large size, the caesium cation has a rare coordination mode with both the phosphorus and oxygen atoms of the 2lambda-3-phospha-1-enolate, forming infinite polymeric chains in the solid state of 15. Two tert-butyl groups in the vicinal positions of compounds 7, 9, 10, 12 and 15 dictate the gauche conformations in compounds 7, 9, 10, 12 and 15, enforcing this stereoselectivity around the C-C-C portion of the rings in the enlargement reaction.

A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp(i)(Pr(4)))Ru(CO)(2)H (Cp(i)(Pr(4)) = C(5)(i-C(3)H(7))(4)H) was prepared from the reaction of Ru(3)(CO)(12) with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp(i)(Pr(4)))Ru(CO)(2)H was determined by X-ray crystallography. The ruthenium hydride complex (C(5)Bz(5))Ru(CO)(2)H (Bz = CH(2)Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)(2)](2), was produced from the reaction of 1,2,3-trimethylindene with Ru(3)(CO)(12), and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)(2)](2)-(mu-H)}(+)OTf (-). A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)(3), PCy(3), PMe(3), P(p-C(6)H(4)F)(3)] were prepared by reaction of Cp(CO)(2)RuH with added L. Protonation of (Cp(i)(Pr(4)))Ru(CO)(2)H, Cp*Ru(CO)(2)H, or CpRu(CO)[P-(OPh)(3)]H by HOTf at -80 degrees C led to equilibria with the cationic dihydrogen complexes, but H(2) was released at higher temperatures. Protonation of CpRu[P(OPh)(3)](2)H with HOTf gave an observable dihydrogen complex, {CpRu[P-(OPh)(3)](2)(eta(2)-H(2))}(+)OTf (-) that was converted at -20 degrees C to the dihydride complex {CpRu[P(OPh)(3)](2)(H)(2)}(+)OTf (-). These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H(2) (750 psi) at 110 degrees C.

[(Ph(3)P)(3)Rh(F)] reacts with CF(3)SiMe(3) to produce trans-[(Ph(3)P)(2)Rh(CF(2))(F)] (1; X-ray), which is equilibrated with a number of species in solution. Addition of excess Ph(3)P shifts all of the equilibria to [(Ph(3)P)(3)Rh(CF(3))] (2; X-ray) as the only NMR-observable and isolable (84%) species. Complex 2 is uniquely highly fluxional in solution, maintaining ligand exchange even at -100 degrees C (12.1 s(-1)). Activation parameters have been determined (variable-temperature (31)P NMR) for the similar but slower exchange in the Me analogue of 2, [(Ph(3)P)(3)Rh(CH(3))]: E(a) = 16.5 +/- 0.6 kcal mol(-1), DeltaG(double dagger) = 12.9 kcal mol(-1) (calculated at -30 degrees C), DeltaH(double dagger) = 16.0 +/- 0.6 kcal mol(-1), and DeltaS(double dagger) = 12.8 +/- 2.3 e.u. Intramolecular exchange in [(R(3)P)(3)Rh(X)] occurs (DFT, MP2//BP86) via a distorted trigonal transition state (TS) with X in an axial position trans to a vacant site. The rearrangement is governed by a combination of steric and electronic factors and is facilitated by bulkier ligands on Rh as well as by strongly donating X that stabilize the TS. The Rh atom in [(H(3)P)(3)Rh(X)] has been shown to be more negatively charged (NPA) for X = CF(3) than for X = CH(3), despite the strongly oppositely charged carbon atoms of the CF(3) (+0.79e) and CH(3) (-0.96e) ligands. Clarification of stereochemical rigidity (X = halide, CN, OR, NR(2)) versus fluxionality (X = H, Alk, Ar, CF(3)) is provided, along with a resolution of the long-standing contradiction between the electron-withdrawing effect of CF(3) in organic compounds and its strong trans influence (electron donation) in metal complexes.

Complexes trans-[(Py)(2)Pd(Ph)(F)] (1; Py = pyridine) and trans-[(t-BuPy)(2)Pd(Ph)(F)] (2; t-BuPy = 4-tert-butylpyridine) have been prepared from the corresponding iodides and AgF. Thermal decomposition of 1 and 2 in anhydrous benzene at 80 degrees C did not result in C-F bond formation, but Pd black and Ph(2) were produced instead, along with novel difluorides trans-[(Py)(2)Pd(F)(2)] (3) and trans-[(t-BuPy)(2)Pd(F)(2)] (4). Both 3 and 4, the first trans-difluoro d(8) square complexes, were independently synthesized from the corresponding diiodides and AgF and fully characterized. Contrary to filled/filled d(pi)-p(pi) repulsion considerations, the Pd-F bond distances in 3 and 4 are unprecedentedly short, being only 1.947(4)-1.958(4) A and shorter than those in 1 and 2 by 0.12-0.13 A. The mechanism of formation of 3 and 4 and bonding in these complexes are discussed.

New compounds of the type R(2/3-x)Rh(2)O(4) with the CaFe(2)O(4) structure have been prepared, where R is a rare earth. For crystals grown in a Bi/V/O flux, the rare earth was partially replaced by Bi. No evidence of ordering of the A cation vacancies is found, but the A cations are displaced from the ideal A cation site by about 0.24 A. Electrical conductivity measurements on crystals suggest that the materials are degenerate semiconductors with Seebeck measurements showing p-type behavior. This is consistent with our observation that x in R(2/3-x)Rh(2)O(4) ranges up to about 0.09. The compounds were also characterized by magnetic susceptibility and diffuse reflectance measurements.

The first stable enols in 1,2-dihydrophosphetes and were synthesized and structurally characterized with intermolecular hydrogen bonds to phosphoryl groups in 10-membered dimeric structures; in contrast, trivalent analogue exists in keto-form, where such stabilization by hydrogen bonds is not feasible.

Generalised undernutrition is common in hospital patients and in the community. It is frequently unrecognised and is associated with a range of adverse consequences that contribute to increased morbidity and mortality. The National Institute for Health and Clinical Excellence recommends that all individuals engaging with healthcare or admitted to residential homes in the community should be screened for undernutrition. Laboratory investigations have little place in the diagnosis of undernutrition: this is primarily a clinical process. In particular, the measurement of serum albumin concentration, though widely promulgated in the past as an index of nutritional status, is worthless for this purpose. Laboratory investigations are, however, of importance: to diagnose specific nutritional deficiencies (eg, of trace elements) and to monitor the provision of nutritional support, to detect metabolic complications and to assess its adequacy (for which the measurement of serum prealbumin concentrations, particularly in conjunction with measurements of C-reactive protein, may be of value).

Use of a superbase in the Favorskii rearrangement of 12 resulted in the synthesis of highly sterically hindered olefins, (E)-2- tert-butyl-4,4-dimethyl-pent-2-enoic acid (4) and (Z)-2- tert-butyl-4,4-dimethyl-pent-2-enoic acid (3).

The first tetra-substituted non-fused chrysene, 3,6,9,12-tetrakis(4-tert-butylphenyl)chrysene with blue electroluminescence at 450 nm, and with a radiance of 500 cd m(-2), was synthesized by a two-step procedure: direct bromination of chrysene in trimethyl phosphate, followed by palladium-catalyzed cross-coupling of tetrabromochrysene and tert-butylphenylboronic acid .

Reaction paths leading to palladium catalyst deactivation during cyanation of haloarenes (eq 1) have been identified and studied. Each key step of the catalytic loop (Scheme 1) can be disrupted by excess cyanide, including ArX oxidative addition, X/CN exchange, and ArCN reductive elimination. The catalytic reaction is terminated via the facile formation of inactive [(CN)4Pd]2-, [(CN)3PdH]2-, and [(CN)3PdAr]2-. Moisture is particularly harmful to the catalysis because of facile CN- hydrolysis to HCN that is highly reactive toward Pd(0). Depending on conditions, the reaction of [(Ph3P)4Pd] with HCN in the presence of extra CN- can give rise to [(CN)4Pd]2- and/or the remarkably stable new hydride [(CN)3PdH]2- (NMR, X-ray). The X/CN exchange and reductive elimination steps are vulnerable to excess CN- because of facile phosphine displacement leading to stable [(CN)3PdAr]2- that can undergo ArCN reductive elimination only in the absence of extra CN-. When a quaternary ammonium cation such as [Bu4N]+ is used as a phase-transfer agent for the cyanation reaction, C-N bond cleavage in the cation can occur via two different processes. In the presence of trace water, CN- hydrolysis yields HCN that reacts with Pd(0) to give [(CN)3PdH]2-. This also releases highly active OH- that causes Hofmann elimination of [Bu4N]+ to give Bu3N, 1-butene, and water. This decomposition mode is therefore catalytic in H2O. Under anhydrous conditions, the formation of a new species, [(CN)3PdBu]2-, is observed, and experimental studies suggest that electron-rich mixed cyano phosphine Pd(0) species are responsible for this unusual reaction. A combination of experimental (kinetics, labeling) and computational studies demonstrate that in this case C-N activation occurs via an S(N)2-type displacement of amine and rule out alternative 3-center C-N oxidative addition or Hofmann elimination processes.

A beta-oxaphosphoniumbetaine stabilized by two tert-butyl groups at the phosphonium part of the betaine and two trifluoromethyl groups at the carbon adjoined to the oxa part of the betaine was isolated and structurally characterized. Additional stabilization results from the solvation of the betaine by a parent phosphonium salt, as in 4, or by protonation with methanol, as in 10. According to X-ray analysis, the betaine exhibits a sterically strained "gauche" conformeric form, with torsion angles in the P-C-C-O moiety of 32.2 degrees for 4 and 28.1 degrees for 10. The P...O separations of 3.121 A for 4 and 3.086 A for 10 are just under the sum of the O and P van der Waals radii (3.32 A). The fast H/D exchange of alpha hydrogen atoms to the phosphonium center was observed in the solution of 10 in deuterium oxide and MeOH-d4. The beta-oxaphosphoniumbetaine has long been suspected as an intermediate in the Wittig reaction, but this is the first time a stabilized derivative has been isolated.

Novel nonfluorinated Cu(diketiminate)L complexes with L = neutral olefinic ligand have been prepared as stable, volatile Cu(I) precursors for the deposition of copper films by an atomic layer deposition (ALD) process. Among them, the complexes of 4-a and 5-a are the most volatile and stable at low temperature (55 degrees C). A clean, conformal copper film was deposited at 120 degrees C in an ALD process. These Cu(I) complexes are the first examples of nonfluorinated copper(I) diketiminates that can be readily applied to an industrial microelectronic fabrication process.

Facile and highly selective perfluoroalkyl-aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50-80 degrees C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by rigid cis-chelating ligands such as dppe are completely unreactive at temperatures up to 130-140 degrees C. Decomposition of [(Ph3P)2Pd(Ph)CF3] in the presence of PhI in benzene at 60 degrees C does not produce PhCF3 but rather leads to [(Ph3P)2Pd(Ph)I] and [Ph4P]+[(Ph3P)Pd(CF3)3]- in a 2:1 ratio with high selectivity.

An application of the new sterically hindered electron-poor 2-(3,5-bis(trifluoromethyl)phenyl)-4-trifluoromethylpyridine [HC--N] (1) in the one-step high temperature cyclometalation by Ir(III)Cl3 in the presence of Ag(I)OC(O)CF3 resulted in the synthesis of tris-cyclometalated complexes [C--N]2Ir[C--C] (3) and [C--N]3Ir (5). A neutral silver cluster with a repeating unit of hexa-silver groups in an infinite chain of (2) was isolated from the above reaction as well. When this cyclometalation was carried out in trimethylphosphate at lower temperature, bis-cyclometalated derivatives [C--N]2Ir(mu-Cl)2Ir[CN]2 (6), [C--N]2Ir[eta2-(O(C((t)Bu))2CH] (7), and [C--N]2Ir(mu-O-P(OMe)2-O)2Ir[C--N]2 (8) were synthesized. According to X-ray analyses complex (3), while trivalent, contains four cyclometalated single Ir-C bonds. One of the Ir-C bonds, next to the nitrogen atom of the CC pyridinium ligand, was found to be the shortest to date (1.977(4) angstroms) for a single bond between iridium and carbon atoms. The coordination of the C--C ligand in (3) to iridium has a decidedly interesting bonding pattern and can be explained by various formulations. The first one is considering this ligand as a monoanionic chelating ligand, in which the second coordination site arises from a carbene or azomethine ylide. Overall the best single picture may be a dianionic ligand making two normal Ir-C bonds, in which the ligand just happens to contain a pyridinium function that compensates for one negative charge on the iridium. LEDs constructed with compounds (7) and (8) give blue-green emission with peak electroluminescent efficiency of 15 and 2 cd A(-1), respectively. An LED constructed with compound (5) gives a yellowish emission with peak electroluminescent efficiency of 5.5 cd A(-1).

A series of new complexes [(L-L)Pd(Ar)(CF3)] (L-L = dppe, dppp, tmeda; Ar = Ph, p-Tol, C6D5) have been synthesized and fully characterized in solution and in the solid state. Remarkable Ph-X activation (X = I, Cl) by [(dppe)Pd(Ph)(CF3)] (1) has been found to come about to cleanly produce biphenyl and [(dppe)Pd(Ph)(X)]. This reaction does not take place under rigorously anhydrous conditions but in the presence of traces of water it readily occurs, exhibiting an induction period and being zero order in PhI. As shown by mechanistic studies, the role of water is to promote reduction of small quantities of the Pd(II) complex to Pd(0) which activates the Ph-X bond. Subsequent transmetalation to give diphenyl Pd complexes, followed by Ph-Ph reductive elimination give rise to the observed products. The water-induced reduction to catalytically active Pd(0) has been demonstrated to proceed via both the Pd(II)/P(III) to Pd(0)/P(V) redox mechanism and alpha-F transfer, followed by facile hydrolysis of the difluorocarbene to carbonyl, migratory insertion, and reductive elimination of PhC(X)O (X = F, OH, or OOCPh). In the absence of H2O and ArX, the diphosphine-stabilized trifluoromethyl Pd phenyl complexes undergo slow Ph-CF3 reductive elimination under reinforcing conditions (xylenes, 145 degrees C).

A bimetallic carbene complex architecture that incorporates a cyclopentadienyl-annulated imidazol-2-ylidene moiety is characterized. The ligand architecture enables direct electronic interaction between the pi- and sigma-bonded metals. A preliminary example of aqueous Suzuki coupling employing a metallocene-fused imidazol-2-ylidene-derived catalyst is described.

The fluoride congener of Wilkinson's catalyst, [(Ph(3)P)(3)RhF] (1), has been synthesized and fully characterized. Unlike Wilkinson's catalyst, 1 easily activates the inert C-Cl bond of ArCl (Ar = Ph, p-tolyl) under mild conditions (3 h at 80 degrees C) to produce trans-[(Ph(3)P)(2)Rh(Ph(2)PF)(Cl)] (2) and ArPh as a result of C-Cl, Rh-F, and P-C bond cleavage and C-C, Rh-Cl, and P-F bond formation. In benzene (2-3 h at 80 degrees C), 1 decomposes to a 1:1 mixture of trans-[(Ph(3)P)(2)Rh(Ph(2)PF)(F)] (3) and the cyclometalated complex [(Ph(3)P)(2)Rh(Ph(2)PC(6)H(4))] (4). Both the chloroarene activation and the thermal decomposition reactions have been shown to occur via the facile and reversible F/Ph rearrangement reaction of 1 to cis-[(Ph(3)P)(2)Rh(Ph)(Ph(2)PF)] (5), which has been isolated and fully characterized. Kinetic studies of the F/Ph rearrangement, an intramolecular process not influenced by extra phosphine, have led to the determination of E(a) = 22.7 +/- 1.2 kcal mol(-)(1), DeltaH(++) = 22.0 +/- 1.2 kcal mol(-)(1), and DeltaS(++) = -10.0 +/- 3.7 eu. Theoretical studies of F/Ph exchange with the [(PH(3))(2)(PH(2)Ph)RhF] model system pointed to two possible mechanisms: (i) Ph transfer to Rh followed by F transfer to P (formally oxidative addition followed by reductive elimination, pathway 1) and (ii) F transfer to produce a metallophosphorane with subsequent Ph transfer to Rh (pathway 2). Although pathway 1 cannot be ruled out completely, the metallophosphorane mechanism finds more support from both our own and previously reported observations. Possible involvement of metallophosphorane intermediates in various P-F, P-O, and P-C bond-forming reactions at a metal center is discussed.

The reaction between 2-(2,3,4,5-tetramethyl-cyclopenta-1,3-dienyl)-pyridine 1 and IrCl3 was performed in an attempt to synthesize a cyclometalated system with decreased pi conjugation in the ligand. An unexpected reduction and rearrangement of bis-pyridinyl-cyclopentadienyl cyclometalated Ir(III) intermediate 2 took place yielding bis-pyridinyl-fulvene Ir(I) complex 4, which exhibits a novel bis-eta1-N,eta2-C,C-binding mode between the pyridinyl-functionalized fulvene ligand and iridium. The iridium atom in 4 is not sandwiched between two cyclopentadienyl moieties; rather, the two cyclopentadienyl groups adopt a pi-pi stacking arrangement with a centroid-centroid distance of 3.494 A. The Cl/P(wedge)O ligand-exchange reaction between 4 and 2-[(diphenylphosphanyl)-methyl]-1,1,1,3,3,3-hexafluoro-propan-2-ol 5 led to loss of one pyridinyl-functionalized fulvene ligand and produced complex 6, in which the remaining pyridinyl-functionalized fulvene ligand exhibits the mono-eta1-N,eta2-C,C-binding mode.

To enhance the volatility of the copper precursor in the copper deposition process, it was envisioned that N,N'-unsymmetrically substituted 1,3-diketimines should be more volatile than their symmetrically substituted counterparts. A variety of Cu(II) (N,N'-unsymmetrically substituted 1,3-diketiminate) complexes have been synthesized and have proven to be much more volatile than their symmetrical counterparts. This makes the new materials particularly attractive to the ALD and CVD processes. Among the new compounds, 8-a and 8-b are sublimable even at room temperature.

[reaction: see text] A series of novel N,N'-unsymmetrically substituted 1,3-diketimines (3, 12, and 27) have been synthesized from the reaction of exocyclic enaminoketones 8 with amines or metalloenamines (from 13 or 14) with imidoyl thioether 25 or 26.

The development of new organic semiconductors with improved electrical performance and enhanced environmental stability is the focus of considerable research activity. This communication presents the design, synthesis, and device stability data for novel bis-5'-alkylthiophen-2'yl-2,6-anthracene organic semiconductors. When incorporated into thin-film field-effect transistors, mobilities as high as 0.5 cm2/Vs and on/off current ratios greater than 107 are observed. We have investigated device stability in terms of both shelf life and operating lifetime. Devices incorporating the reported semiconductors display an average field-effect mobility of 0.4 cm2/Vs for DHTAnt and an on/off current ratio of 106 even after 15 months of storage. Furthermore, there is no decrease in performance during continuous operation of the devices over several thousand cycles.

The fluoro analogue of Wilkinson's catalyst, [(Ph3P)3RhF] (1), was synthesized and fully characterized. Both solution behavior and solid-state geometry parameters of 1 were found to be surprisingly similar to those of Wilkinson's catalyst. Unlike Wilkinson's catalyst however, 1 exhibited most unusual reactivity toward the notoriously inert C-Cl bond of nonactivated chloroarenes. The novel Ph-Cl activation with 1 includes fluorine transfer from the metal to a phosphine ligand and evidently phenyl transfer from the phosphine to Rh to produce an electron-rich sigma-phenylrhodium intermediate.

trans-Cyclopropyl beta-amino acid derivatives can be synthesized in five steps with excellent enantioselectivities using a chiral (Salen)Ru(II) cyclopropanation catalyst in the key asymmetry-induction step. This facile synthesis proceeds with high overall yield and can be used to prepare a number of carbamate-protected (Cbz and Boc are demonstrated) beta-amino acid derivatives.

The syntheses and rat CRF receptor binding affinities of 'retro-pyrazolotriazine' corticotropin-releasing factor (CRF) ligands 4 are reported. Some have high affinity for rat CRF receptors (K(i)< or =10 nM). The data provide additional support for the hypothesis that it is possible to interchange isosteric cores with similar electronic properties in the design of high-affinity CRF receptor ligands, provided the peripheral pharmacophore elements are maintained in the same three-dimensional array.

We determined that the structure of the previously published highly efficient blue electroluminescent borate complex, lithium tetra(2-methyl-8-hydroxyquinolato) boron, does not contain boron. Rather, it is the lithium salt of 2-methyl-8-hydroxyquinoline.

Reaction of 2,2-bis(trifluoromethyl)-1,1-dicyanoethylene (BTF; 1) with 6,6-dimethylfulvene (2) affords the expected Diels-Alder cycloadduct, 7-(1-methylethylidene)-3,3-bis(trifluoromethyl)bicyclo[2.2.1]hept-5-ene-2,2-dicarbonitrile (3), in good yield. The cycloadduct 3 is unstable and exists in equilibrium with the starting materials in less polar solvents. In more polar environment, the [4 + 2] adduct 3 either reverts to starting materials, or, in a competing process, is converted to the formal [2 + 2] adduct, 2-(1-methylethylidene)-7,7-bis(trifluoromethyl)bicyclo[3.2.0]hept-3-ene-6,6-dicarbonitrile (6). In the presence of acid, 3 is converted to a third isomeric form, 1,3a,5,6-tetrahydro-7-methyl-5,5-bis(trifluoromethyl)-4H-indene-4,4-dicarbonitrile (8). Both 6 and 8 are formed with complete regiospecificity. Quantum mechanical calculations and X-ray crystallographic studies of this ensemble of reactions by BTF, and the analogous set of reactions by its progenitor, tetracyanoethylene (TCNE), reveal several interesting facets. The conversion of 3 to 6 occurs in certain polar solvents, in the presence of silica gel and alumina, as well as in the solid state. Single crystals of 3 were observed by X-ray crystallography to undergo crystal-to-crystal rearrangement to 6. The conversion of 3 to 8 proceeds by the initial retro-Diels-Alder reaction followed by isomerization of the fulvene to 1-isopropenyl-1,3-cyclopentadiene that then reacts with BTF to give the alternative Diels-Alder product as a single regioisomer. A hybrid density functional theory (DFT) method at the B3LYP/6-31G(d) level of theory gave calculated relative energies of 0.0, -9.0, and -18.8 kcal/mol for 3, 6, and 8, respectively. The same method was also used to correctly predict the regiochemical outcome of the cycloaddition of BTF with 1-isopropenyl-1,3-cyclopentadiene. Finally, an explanation is offered for the preference of the persubstituted cyanoolefins BTF and TCNE to add to the exocyclic diene portion of 1-isopropenyl-1,3-cyclopentadiene and the contrasting preference of 2-acetyloxy-2-propenenitrile to add to the endocyclic diene.

Large transparent blue crystals of vanadyl pyrophosphate, (VO)(2)P(2)O(7), were grown from a phosphorus pentoxide flux, and the single-crystal X-ray structure of (VO)(2)P(2)O(7) was determined with high precision. On the basis of spin dimer analysis, we examined the spin exchange interactions of (VO)(2)P(2)O(7) and its precursor VO(HPO(4)).0.5H(2)O. Our analysis of (VO)(2)P(2)O(7) using two high-precision crystal structures shows unambiguously that the V3-V4 chain has a larger spin gap than does the V1-V2 chain and that the super-superexchange (V-O...O-V) interaction is stronger than the superexchange (V-O-V) interaction in the V3-V4 chain while the opposite is true in the V1-V2 chain. Our analysis of VO(HPO(4)).0.5H(2)O reveals that the superexchange interaction must dominate over the super-superexchange interaction, in disagreement with the conclusion from a powder neutron scattering study of VO(DPO(4)).0.5D(2)O.

First metal complexes containing the perfluoroacetylacetonato ligand have been prepared by the reaction of anhydrous Ln(OAc)3 (Ln = Eu, Tb, Tm) with heptafluoroacetylacetone, optionally in the presence of other ligands Ph3PO, bpy, and PyO.

The reaction of Fe(II)(C5Me5)(C5H5), FeCpCp, with percyano acceptors, A [A = C4(CN)6 (hexacyanobutadiene), TCNQF4 (perfluoro-7,7,8,8-tetracyano-p-quinodimethane), and DDQ (2,3-dichloro-5,6-dicyanobenzoquinone)], results in formation of 1:1 charge-transfer salts of [Fe(III)CpCp]*]*+[A]*- composition. With A = TCNQ (7,7,8,8-tetracyano-p-quinodimethane) a 1:2 electron-transfer salt with FeCpCp forms. With A = TCNE (tetracyanoethylene) a pair of 1:1 salts as well as a pair of 2:3 salts of [FeCpCp]2[TCNE]3.S (S = CH2Cl2, THF) have been isolated and characterized by single-crystal X-ray diffraction. [FeCpCp][TCNE] consists of parallel 1-D.D(*+)A(*-)D(*+)A(*-)D(*+)A(*-). chains, while [FeCpCp][TCNE].MeCN has a herringbone array of D(*+)A2(2-)D(*+) dimers separated by solvent molecules. Although each [TCNE](-) is disordered, the diamagnetic [TCNE]2(2-) dimer is structurally different from those observed earlier with an intradimer separation of 2.79 A. The [TCNE](-) in the 2:3 [FeCpCp]2[TCNE]3.S exists as an eclipsed diamagnetic [TCNE]2(2-) dimer with an intradimer ethylene C.C separation of 2.833 and 2.903 A for the CH2Cl2- and THF-containing materials, respectively. The bond distances and angles for all the cations are essentially equivalent, and the distances are essentially equivalent to those previously reported for [FeCp2](*+) and [FeCp2](*+) cations. The average Fe-C5H5-ring and Fe-C5Me5-ring centroid distances are 1.71 and 1.69 A, respectively, which are 0.05 A longer than reported for Fe(II)CpCp. The one-electron reduction potential for Fe(II)CpCp is 0.11 V (vs SCE). The 5 K EPR of [FeCpCp](*+)[BF4](-) exhibits an axially symmetric powder pattern with g(parallel) = 4.36 and g(perpendicular) = 1.24, and the EPR parameters are essentially identical to those reported for ferrocenium and decamethylferrocenium. The high-temperature magnetic susceptibility for polycrystalline samples of these complexes can be fit by the Curie-Weiss law, chi = C/(T - theta), with low theta values and mu(eff) values from 2.08 to 3.43 mu(B), suggesting that the polycrystalline samples measured had varying degrees of orientation. [FeCpCp][TCNE] exhibits the highest effective moment of 3.43 mu(B)/Fe and weak ferromagnetic coupling, as evidenced from the theta of 3.3 K; however, unexpectedly, it does not magnetically order above 2 K. The formation of the four phases comprising FeCpCp and TCNE emphasizes the diversity of materials that may form and the present inability to predict neither solid-state compositions nor structure types.

Providing interpretative comments on reports, particularly those for primary care physicians is an important part of our job. Few clinical biochemists (whether medical or scientific) receive significant training for this. Most work in isolation, and few receive feedback on the utility of their comments. Surveys show an extremely wide divergence of opinion and comment even on apparently straightforward sets of abnormal results. Some comments are regarded as highly inappropriate when assessed by peer review. There is a need for further education and training in this area, concentrating as much on 'how to comment' as on 'what to comment'. There is also a need to establish some form of quality assurance for this important part of the post-analytical phase. A pilot External Quality Assurance Scheme (EQAS) is now being established.

Famoxadone is a newly commercialized fungicide and potent Qo-site inhibitor of cytochrome bc1. The S-(-)-enantiomer of famoxadone (the active component) was synthesized by two routes and was analyzed computationally and by X-ray crystallography. The molecule displays an extended conformation with flexibility in the structure imparted by the two terminal phenyl groups. In the crystal lattice, intermolecular hydrogen bonds occur between the NH and the oxygen atoms of the heterocycle.