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Background: Supervised injectable opioid treatment (SIOT) is a promising alternative for people living with opioid use disorder (OUD) who have not sufficiently benefitted from oral opioid substitution treatment. Yet, SIOT utilization remains limited in Germany. We propose that this is due to beliefs, or schemas, on SIOT among people living with OUD. Drawing from medical sociology and social psychology, this study explores the emergence and evolution of such schemas on SIOT. Methods: We conducted semi-structured interviews with 34 individuals currently in or eligible for SIOT in two German outpatient treatment facilities and paralleled an inductive qualitative content analysis with the exploration of individual cases. Results: The analysis revealed that peer-to-peer interaction and individuals’ practical experiences in therapy are crucial in constructing and changing idiosyncratic and shared schemas of SIOT. When facing ambiguous information, cognitive strategies like subtyping served to mitigate uncertainty. Conclusion: This research has important practical implications for integrating experiential knowledge into clinical care and improve information sharing among people living with OUD. A nuanced understanding of the complex network of informal advice-seeking and -giving among people living with OUD is indispensable to adequately expand treatment modalities of proven effectiveness.

ABSTRACTThis paper argues that mainstream economics is a materialist and reductionist science. It criticizes the core assumptions of mainstream economics – namely, the existence of ‘Homo Oeconomicus’ and the goals of profit maximization, economic efficiency, and economic growth; and shows that these goals lead to an economy that is not only unhealthy for people but is making the planet unsustainable. The paper makes a case for the development of a spiritually informed economics. It concludes that by helping to create ecological and human economic practices and policies, spiritually informed economics can support the flourishing of life on Earth (both human and non-human, present and future).

ABSTRACTThis article describes the background to, and focus of, a new and extensive research program being undertaken at the Corvinus Institute for Advanced Studies of the Corvinus University of Budapest, Hungary. Entitled the Economy and Religion Program, it aims to explore and study the multiple roles that religion and spirituality play in the functioning of the economy. It focuses on the contemporary issues of capitalism in relation to ethics and morality; ecology and sustainability; and social inequality and cultural diversity. It is intended to foster a spirit of open dialogue that seeks collaboration across disciplines, cultures and faith traditions.

One of the most reliable predictors of school effectiveness is student engagement, which is not only related to students’ current achievement but also long-term outcomes. Using linear regression and structural equation modeling procedures, the present study was aimed at examining the relationship between dropout risk, dimensions of student engagement, and family background. The survey study involved 3251 7th grade Hungarian students who completed the adapted Student Engagement Instrument and self-reported background questionnaire. According to the results, student performance is mainly related to parents’ educational attainment, but a moderate or weak correlation with behavioral, academic, and cognitive engagement is also detectable. While affective engagement shows a weak association with performance, it correlates with other engagement dimensions linked to achievement. This result suggests that support from parents, peers, and teachers may have an indirect effect on achievement; however, the present study could not confirm this hypothetical model. Based on our data, parental educational attainment and student engagement account for approximately 41 % of student performance which draws attention to the complexity of the relationship between student engagement and performance and highlights the importance of a comprehensive approach to dropout and student engagement in this context.

ABSTRACTThis interview with Peter Pruzan shows his personal and professional journey from optimization to transformation, a path to the wellspring of rationality, ethics and spirituality.

AbstractObjective of this study was to evaluate the effect of supplementation of growing rabbits’ diet with 5% spirulina (Arthrospira platensis) and/or 3% (Thymus vulgarisL.), on composition and amount of rabbits caecal microbiota. After weaning, rabbits were randomly sorted to 4 groups (n = 42/group). The control group received a pellet without any supplementation, in treated groups the dietary supplementation was provided until 77 days of age. On 49, 63 and 77 days of age, six healthy animals/group were randomly selected and slaughtered. From the caecal content the amount of total bacteria, Bacteroides, Clostridium leptumand Clostridium coccoideswere determined by quantitative polymerase chain reaction (qPCR), with the aid of bacterial ribosome coding DNA. The copy number of total bacteria, C. leptum, C. coccoidesand Bacteroides varied between 2.75 × 1012to 2.24 × 1013, 5.25 × 1011to 1.82 × 1012, 2.5 × 1010to 6.91 × 1011 and 5.89 × 1010to 1.10 × 1012, respectively. The amount of investigated bacteria represented 0.6%-13.4% of the total bacteria. The use of spirulina and/or thyme supplements influenced the amount of the copy number of each bacteria examined between 49 and 77 days of age. Their effect on the total bacteria number was temporary. Spirulina resulted in more Bacteroides on day 63 but significantly lower amount of Clostridia at 63 and at 77 days of age. The antimicrobial effect of thyme on the absolute Clostridia number was temporary, prevailing on day 63. Thyme resulted in significantly decreasing percentage ratio (within total bacteria) of C. leptumand C. coccoidesby 77 days of age.

The aim of our cross-sectional investigation was to explore prosocial behavior at the ages of 9, 11, and 13, and to reveal associations between this social behavior and some background variables such as age, gender, and parents' educational attainment. The participants were 185 Hungarian students and their teachers. Two Likert-type questionnaires (teacher and student versions) were developed and used in this study. These instruments proved to be highly reliable (Cronbach's α: .79–.87). The results from both teachers and students indicate that sharing property and showing a positive attitude toward others are more typical of third-graders (age 9) than of older children. Conversely, standing up for individual interests during teamwork is most typical of the oldest group of children. Students and teachers also agree that third (age 9) and fifth graders (age 13) are more likely to help others than older children. The correlation coefficients for the different factors of prosocial behavior become progressively weaker with age. Cooperation and helping appear to become independent of each other. Our regression analyses reveal that parents' educational level explains equally low shares of the variance in the measured areas of the prosocial behavior for all three age groups.

In an in vitroexperiment commercially available probiotic products were tested for the survival of bacteria under conditions of simulated human digestion either when used alone or mixed into yogurt. In the in vivoexperiment the effects of feeding a whey- and milk-based yogurt prepared with the probiotic strain showing adequate survival in the in vitroexperiment, was measured on body weight, feed consumption and immune response of rats (IgG and IgA level after immunisation), on the composition and volatile fatty acid production of the intestinal microbiota and on the structure of intestinal villi. The Lactobacillus acidophilus(LA-15) strain had inadequate surviving ability in rats. Bifidobacterium animalisssp. lactis(BB-12) improved the composition of the intestinal microflora, whereas whey-containing product had a mild immunostimulating effect and exerted a favourable influence on the morphology of intestinal villi. The consumption of yogurts increased the depth of crypts in the ileum, which resulted in enhanced secretion and thus softer faeces.

The caecal chyme of pigs was incubated anaerobically in McDougall buffer with and without fumonisin B1(5 μg/ml) for 0, 24 and 48 h. The plate count agar technique was applied for enumerating the amount of bacteria including aerobic, anaerobic bacteria, coliform, Escherichia coliand Lactobacillussp. The quantitative polymerase chain reaction was also performed to estimate the number of copies of the total bacteria, Lactobacillus, Bacteroidesand Prevotella. No significant differences in the amount of bacterial groups between the experimental (buffer, chyme, and fumonisin B1) and control 1 groups (buffer + chyme) were observed in both methods. Fumonisin B1and hydrolysed fumonisin B1concentration were analysed by liquid chromatograghy – mass spectrometry. There was no significant difference in FB1concentration between the experimental and the control 2 group (buffer and fumonisin B1) at 0 h incubation, 5.185 ± 0.174 μg/ml compared with 6.433 ± 0.076 μg/ml. Fumonisin B1concentration in the experimental group was reduced to 4.080 ± 0.065 μg/ml at 24 h and to 2.747 ± 0.548 μg/ml at 48 h incubation and was significantly less than that of in the control group. Hydrolysed fumonisin B1was detected after 24 h incubation (0.012 ± 0 μg/ml). At 48 h incubation time, hydrolysed fumonisin B1concentration was doubled to 0.024 ± 0.004 μg/ml. These results indicate that fumonisin B1can be metabolised by caecal microbiota in pigs though the number of studied bacteria did not change.

In an in vitroexperiment commercially available probiotic products were tested for the survival of bacteria under conditions of simulated human digestion either when used alone or mixed into yogurt. In the in vivoexperiment the effects of feeding a whey- and milk-based yogurt prepared with the probiotic strain showing adequate survival in the in vitroexperiment, was measured on body weight, feed consumption and immune response of rats (IgG and IgA level after immunisation), on the composition and volatile fatty acid production of the intestinal microbiota and on the structure of intestinal villi. The Lactobacillus acidophilus(LA-15) strain had inadequate surviving ability in rats. Bifidobacterium animalisssp. lactis(BB-12) improved the composition of the intestinal microflora, whereas whey-containing product had a mild immunostimulating effect and exerted a favourable influence on the morphology of intestinal villi. The consumption of yogurts increased the depth of crypts in the ileum, which resulted in enhanced secretion and thus softer faeces.

The caecal chyme of pigs was incubated anaerobically in McDougall buffer with and without fumonisin B1(5 μg/ml) for 0, 24 and 48 h. The plate count agar technique was applied for enumerating the amount of bacteria including aerobic, anaerobic bacteria, coliform, Escherichia coliand Lactobacillussp. The quantitative polymerase chain reaction was also performed to estimate the number of copies of the total bacteria, Lactobacillus, Bacteroidesand Prevotella. No significant differences in the amount of bacterial groups between the experimental (buffer, chyme, and fumonisin B1) and control 1 groups (buffer + chyme) were observed in both methods. Fumonisin B1and hydrolysed fumonisin B1concentration were analysed by liquid chromatograghy – mass spectrometry. There was no significant difference in FB1concentration between the experimental and the control 2 group (buffer and fumonisin B1) at 0 h incubation, 5.185 ± 0.174 μg/ml compared with 6.433 ± 0.076 μg/ml. Fumonisin B1concentration in the experimental group was reduced to 4.080 ± 0.065 μg/ml at 24 h and to 2.747 ± 0.548 μg/ml at 48 h incubation and was significantly less than that of in the control group. Hydrolysed fumonisin B1was detected after 24 h incubation (0.012 ± 0 μg/ml). At 48 h incubation time, hydrolysed fumonisin B1concentration was doubled to 0.024 ± 0.004 μg/ml. These results indicate that fumonisin B1can be metabolised by caecal microbiota in pigs though the number of studied bacteria did not change.

Fluid simulations today are remarkably realistic. In this Comment I discuss some of the most striking results from the past 20 years of computer graphics research that made this happen.

The application of the Pd/Al2O3catalyst in allyl alcohol isomerization and subsequent aldol condensation and heterocyclization reactions is described. The activity of Pd/Al2O3in these transformations is suggested to be due to the participation of the Lewis acidic sites of the support in the activation of the alcohol towards oxidative dehydrogenation by the metal and subsequent hydride transfer. The resulting enol(ate)/aldehyde could undergo further reactions promoted by the acid–base properties of the support. In the aldol condensation reactions of the isomerization product, electron poor aromatic aldehydes and heteroaromatic aldehydes showed the highest activity, while aromatic aldehydes bearing electron donating substituents reacted after transformation to the corresponding N-tosyl imines. 1,2-Disubstituted aromatics gave heterocyclic products in one-pot multistep reaction sequences.

The paper presents an operationalised model for responsible decision making in corporate context. The starting point is Kenneth E. Goodpaster's conception of moral responsibility. Basic empirical findings of decision psychology are used to arrive at a robust model of making responsible decisions. In the proposed model decision alternatives are simultaneously evaluated from different value perspectives. Responsible decision making is defined as finding the least worst alternative in the multidimensional decision space of deontological, goal-achievement, and stakeholder values. Some character traits of the responsible decision maker are also provided.

A prevention-oriented, two-year school-based program for seven-year-olds to facilitate the development of social competence was designed and tested. Conducted by a trained psychologist, the program focused on three groups of social skills and behaviors (interpersonal, self-related and task-related). The authors applied a new theoretical framework for the interpretation of our findings, that of ‘criterion referenced education’. The main idea of this new concept is that training will not be stopped until each and every child reaches optimal acquisition and mastery of skills and abilities. In one third of the subjects involved in the experiment the two-year development resulted in the optimal acquisition of the studied skill group. The results confirmed our hypothesis that social skills can be developed effectively in a school context and that criterion referenced education can be used for developing social skills with success.

The synthesis of a series of tripod ligands MeOCH2C(CH2X)(CH2Y)(CH2Z) (X = PR2; Y, Z = PR'2 or pz; pz = 1-pyrazolyl) based on the 3,3-difunctionalized oxetane O^a[CH2]2C^a(CH2OMs)(CH2Br)(O^a−C^a) as the starting material is described. With their mixed donor sets these ligands coordinate to d⁸-metal ions in a bidentate binding mode. One of the three donors remains uncoordinated in each case. Coordination of phosphane donors is generally preferred over coordination of pyrazole donors. With bulky phosphanes such as −CH2PMes2, however, pyrazole may compete with PR2, depending on the kind of the d⁸ fragment. Dynamic exchange between coordinated and noncoordinated pyrazole donors is observed. Tetracoordinate complexes of the general type L2MR2 are formed (L2 symbolizes the tripod ligand in its bidentate chelate binding mode with two donors functions coordinating and the third one serving as a dangling arm; M = Ni^II, Pd^II, Pt^II). With nickel(II) as the d⁸ species, tetrahedral or square-planar coordination geometries ensue, depending on the kind of donor functions and on the kind of co-ligands R. With palladium(II) and platinum(II) as the d⁸ centres, square-planar coordination is observed throughout. The size of the chelate cycles varies from six to eight depending on the number of pyrazole entities within the cycle. The conformations and the conformational flexibility characterizing the chelate cycles have been analysed by X-ray analyses and by variable-temperature NMR. The classes of conformations observed may be formally reduced to chair, half-chair and twist-boat conformations. Dynamic exchange between these conformations is observed. In one case, the same compound forms two different types of crystals that differ by the conformation adopted by their chelate cycles. All compounds have been fully characterized by standard analytical techniques including X-ray structure analysis of 14 chelate compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

[Cu(phen)2(fla)]ClO4 was prepared by treating [Cu(CH3CN)4]ClO4 with flavonol (flaH) in the presence of 1,10-phenanthroline (phen) as a co-ligand. Its oxygenation in DMF (or CH3CN) solution at elevated temperature gave the (O-benzoylsalicylato)copper(II) complex [Cu(phen)2(O-bs)]ClO4 (bs = benzoylsalicylato) and carbon monoxide via an endoperoxide intermediate. Crystallographic characterisation of [Cu(phen)2(O-bs)]ClO4 as the CH2Cl2 solvate [triclinic, space group P$\bar 1$ , a = 10.499(3) Å, b = 12.556(4) Å, c = 17.094(5) Å, α = 72.69(2), β = 89.35(2), γ = 69.19(2)°, V = 1999.7(10) ų, Z = 2, R1 = 0.0962] shows that the molecule has a distorted trigonal-bipyramidal structure (τ = 0.96). The oxygenolysis was monitored by spectrophotometry, and the pseudo-first-order rate constant k'phen was found to be (2.47 ± 0.11) × 10⁻⁴ s⁻¹ at 120 °C. Complexes of [Cu(L)(4'R-fla)2] (L = phen, bpy, TMEDA; R = H, OCH3, CH3, Cl) were also prepared by treating the complexes Cu(4'R-fla)2 with nitrogen-containing co-ligands. Their oxygenation resulted in the corresponding complexes Cu(L)(2HOpg)2 (2HOpg =2-hydroxyphenylglyoxylate) derived by spontaneous hydrolysis of Cu(L)(bpg)2 (bpg = 2-benzoatophenylglyoxylate). The (phenylglyoxylato)copper complexes were probably formed via 1,2-dioxetan intermediates, since the oxygenation of Cu(phen)(fla)2 showed chemiluminescence with bands at 506, 546, and 578 nm in the emission spectrum due to the decomposition of a 1,2-dioxetan species. Labelling experiments with an ¹⁸O2/¹⁶O2 mixture (1:3) showed the incorporation of both ¹⁸O atoms of ¹⁸O2 into the flavonolate ligand. The kinetics of the oxygenolysis of Cu(L)(fla)2 gave rate constants according to the rate law −d[Cu(L)(4'R-fla)2]/dt = k[Cu(L)(4'R-fla)2][O2]: k/M⁻¹ s⁻¹ = (9.50 ± 0.60) × 10⁻² (L = phen), (2.40 ± 0.10) × 10⁻² (L = bpy), (2.00 ± 0.10) × 10⁻² (L = TMEDA) M⁻¹ s⁻¹ at 353.16 K. The oxygenolysis of the complexes Cu(phen)(4'R-fla)2 fits a Hammett linear free energy relationship and an increase of the electron density on the copper ion makes the oxygenation reaction faster. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

The title compounds 3‐5are accessible by treatment of P(C6H4CH2NMe2‐2)3(1) with CuX (2a: X = Cl, 2b: X = Br, 2c: X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1with equimolar amounts of 2aaffords the copper(I) chloride [P(C6H4CH2NMe2‐2)3]CuCl (3). With a further equivalent of 2ahomobimetallic [P(C6H4CH2NMe2‐2)3]Cu2Cl2(4) is formed, which also can be synthesized by the reaction of 1with two equivalents of 2a. Complex 3reacts with CuX (X = Br, I)to afford [P(C6H4CH2NMe2‐2)3]Cu2ClX (5a: X = Br; 5b: X = I) in which mixed halides are present. The newly synthesized complexes 3‐5were characterized by elemental analyses, by their IR‐, 1H‐, 13C{1H}‐ and 31P{1H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3and 4are reported. Mononuclear 3crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å 3and Z = 4 with 4053 observed unique reflections; R1= 0.0314. The crystal structure of 3consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4crystallizes in the monoclinic space group P21/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; 3and Z = 4 with 9021 observed unique reflections; R1= 0.0480. In 4one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu2Cl2segment resembles to a building block which is set up by a contact ion pair consisting of Cu+and [CuCl2]‐, respectively.

Dicyanomethanides, [RC(CN)2]⁻ (1⁻), are bridging ligands with an angular clamp-type shape. In the tripod/iron(II) system, [tripod = CH3C(CH2PPh2)3], they form binuclear species with three of the clamp-type ligands bridging two iron centers. An appropriate stoichiometric mixture of the tripod ligand, iron(II) salts and the dicyanomethanide ligand leads to the exclusive formation of [tripodFe{μ-NC−C(R)−CN}3Fetripod]⁺ (3⁺). Altogether, seven constituent groups arrange themselves in this type of aggregate. The process of self-aggregation is distinctly modified by the presence of cyanide ions that may act as linear rod-type bridging ligands. Equimolar mixtures of tripod, iron(II) salts, dicyanomethanide ligands and cyanide form tetranuclear aggregates [{tripodFe}3{μ-NC−C(R)−CN}3{μ-CN}3FeX]⁺ (5⁺). In these species, the iron centers form a trigonal-pyramidal arrangement with three octahedrally coordinated low-spin tripodiron(II) entities in the basal plane and a tetrahedrally coordinated high-spin iron(II) at the apex. The iron centers in the basal plane are connected by μ²-bridging dicyanomethanide ligands. The apical iron center is coordinated by the N-termini of three cyano ligands, which complete the octahedral coordination of the basal low-spin iron(II) centers. The fourth, external ligand X at the tetrahedrally coordinated high-spin iron(II) apex can be varied, but in most cases it is found to be a terminally coordinated dicyanomethanide entity. Without counting this variable ligand X, thirteen constituent groups of four different types selectively aggregate to form the cage compounds 5⁺. While the dinuclear compounds 3⁺ are diamagnetic, the tetranuclear species 5⁺ have magnetic moments close to the spin-only value of μs.o. = 4.9 μB, for tetrahedral high-spin iron(II). The Mössbauer spectra are in agreement with the description of 5⁺ above, which contain three low-spin tripodiron(II) entities and one high-spin iron(II) center. The synthesis, spectroscopic data, cyclic voltammetric data, Mössbauer data and X-ray analytical data for a series of compounds of types 3⁺ and 5⁺ are presented in this paper.

Treatment of the tripod compounds tripodCoCl2 (1), and tripodCoCl (2), [tripod = CH3C(CH2PPh2)3] in THF solution under argon atmosphere with strong reducing agents such as KC8 leads to the generation of reactive species. While the dinitrogen compound tripodCo(N2)Cotripod (3), which is formed under N2 atmosphere, is rather unreactive, the species formed under argon atmosphere undergo selective reactions with compounds containing P−H or Sn−H functions. With PhPH2 as the reagent, the diphosphene compound tripodCo(η²-PhP=PPh) (8), is formed in a yield (44%) similar to that achieved in the preparation of 8 from 2 and PhPHNa (60%). With Ph3SnH as the reagent, tripodCoSnPh3 (9), is obtained (yield 61%), while reaction with Bu3SnH produces tripodCo(H)2SnBu3 (10a, 50%). The Co^I species 9 undergoes oxidative addition of dihydrogen to produce the Co^III compound tripodCo(H)2SnPh3 (10b), which is an analogue of 10a. The properties of these new compounds are characterized by the usual analytical techniques, including NMR spectroscopy, cyclic voltammetry, and X-ray analysis.

The synthesis and characterization of the di-, tetra-, and hexanuclear titanium(IV)−copper(I) carboxylates {[Ti](C&tbd1;CSiMe3)2}CuO2CR² (3) {3a:  R² = Me, 3b:  R² = C6H5, 3c:  R² = CH2C6H5, 3d:  R² = CH&dbd;CMe2; [Ti] = (η⁵-C5H4SiMe3)2Ti}, {[Ti](C&tbd1;C^tBu)2}CuOC(O)−X−C(O)OH [12a:  X = trans-CH&dbd;CH, 12b:  X = CH2C(&dbd;CH2)], {[Ti](C&tbd1;C^tBu)2}CuOC(O)−X−C(O)OCu{(R¹C&tbd1;C)2[Ti]} [R¹ = ^tBu, 13a:  X = trans-CH&dbd;CH, 13b:  X = cis-CH&dbd;CH, 13c:  X = 1,4-C6H4, 13d:  X = C&tbd1;C, R¹ = SiMe3, 14a:  X = trans-CH&dbd;CH, 14b:  X = CH2C(&dbd;CH2)], [{[Ti](C&tbd1;C^tBu)2}CuO(O)C]2 (13e) as well as {[Ti](C&tbd1;C^tBu)2}CuO(O)C-1-C6H3(CO2H)2-3,5 (16), [{[Ti](C&tbd1;C^tBu)2}CuO(O)C]2-1,3-C6H3(CO2H)-5 (17), and [{[Ti](C&tbd1;C^tBu)2}CuO(O)C]3C6H3-1,3,5 (18) is described. All of these complexes are easily accessible by the reaction of {[Ti](C&tbd1;CR¹)2}CuMe (1a:  R¹ = SiMe3, 1b:  R¹ = ^tBu) with the corresponding carboxylic acids in different stoichiometric ratios of the reactants. Furthermore, the preparation and reaction chemistry of the alkyne-stabilized copper(I) percarboxylate {[Ti](C&tbd1;CSiMe3)2}CuO2C(O)C6H4Cl-3 (10) is discussed. As the central organic building block, all complexes contain mono-, di-, or tricarboxylic units. The latter two allow for the subsequent addition of further titanium(IV)−copper(I) assemblies onto these entities. The X-ray structure analyses of 3a and 13a are reported. Within the {[Ti](C&tbd1;CR¹)2}CuOC(O)R² array the copper(I) center is η²-coordinated by both R¹C&tbd1;C groups of the organometallic tweezer [Ti](C&tbd1;CR¹)2 and η¹-bonded by one oxygen atom of the O2CR² unit. Cyclic voltammetric studies on representative examples are presented and discussed comparatively.

The triphos ligand CH3C(CH2PPh2)3reacts with Co(BF4)2(aq) or Fe(BF4)2(aq) in the presence of nitriles RCN to produce the pentacoordinate [triphosCo(NCR)2](BF4)2(1) or the hexacoordinate [triphosFe(NCR)3](BF4)2(2). With α,ω-dinitriles NC-X-CN dinuclear compounds [triphosFe(NC-X-CN)3Fetriphos](BF4)4(X = (CH2)3(3a) X = o-C6H4(3b) are formed. The compound [triphosFe((CH3)2C=C(CN)2)3Fetriphos](PF6)4(3c) is obtained from FeCl2by addition of the triphos ligand, the dinitrile and NaPF6.

CH3C(CH2PPh2)3CoCl (1) is easily accessible from CH3C(CH2PPh2)3CoCl2 by reduction with activated zinc powder. Upon dehalogenation with TlPF6, 1 reacts with dienes to give [tripodCo^I-(η⁴-diene)]⁺ (2). The heterodienes acrolein and methyl vinyl ketone produce the analogous η⁴-heterodiene compounds 3. When crotonaldehyde is used as the potential η⁴-diene ligand, decarbonylation is observed leading to [tripodCo^I-(CO)2]⁺ (4). Reaction of [tripodCoaq](BF4)2 with allyl mercaptan produces [tripodCo^I-(η⁴-thioacrolein)]⁺ (3a) through dehydrogenation of the ligand precursor. 1,2-Diketones such as benzil and phenanthrenequinone do not coordinate in a η⁴ fashion but rather generate η²-coordinate enediolato ligands by an electron-transfer process, resulting in compounds of the type {tripodCo^III-[η²-RC(O)=C(O)R]}⁺ (5). All the compounds have been characterized by standard analytical and spectroscopic techniques, including X-ray analysis in some cases. Compounds 4 and 5 show trigonal-bipyramidal coordination in the solid state, whereas the coordination polyhedra in compounds 2 and 3 are better described as square-pyramidal. While a minimum of two phosphorus resonances might be expected for each of these coordination geometries, only one time-averaged signal is normally observed. Only with the η⁴-coordinated heterodienes acrolein, methyl vinyl ketone, and thioacrolein present in 3 is there a resolution of the signals of the three chemically distinct phosphorus nuclei at low temperatures. By ³¹P-NMR line-shape analysis, the activation barriers for the rotational reorientation of the heterodienes are found to be around ΔH^≠ = 47 kJmol^–1 for all three compounds 3.

The tripodal ligand [CH3C(CH2C5H4)(CH2PPh2)2]^– reacts with RuCl2(PPh3)3 to produce CH3C(CH2-η⁵-C5H4)(CH2-η¹-PPh2)2RuCl, [tripodCpL2RuCl], 1. Complex 1 undergoes substitution of the chlorine function with various nucleophiles L' to produce [tripodCpL2RuL']⁺. The carbonyl derivative (L' = CO) 2, isonitrile (L' = RNC) 3, nitrile compounds (L' = RCN) 4, and a tolane adduct (L' = η²-PhC≡CPh) 5 are obtained when 1 is treated with the appropriate ligands in polar solvents. Halide acceptors (e.g. TlPF6) are generally needed to promote these reactions. The cyanide derivative tripodCpL2RuCN (3a) is alkylated by F3CSO3CH3 to give the isonitrile derivative [tripodCpL2RuCNMe]⁺3b. Terminal alkynes HC≡CR produce vinylidene compounds [tripodCpL2RuL']⁺, where L' = C=CHR (R = tBu, 7b; R = Ph, 7c), or allenylidene derivatives, L' = C=C=CPh2 (6), depending on the nature of R (R = CPh2OH for synthesis of 6). Trimethylsilylacetylene gives the parent vinylidene species, L' = C=CH2 (7a), which is transformed to the Fischer-type carbene compound, L' = C(OMe)Me (8), upon treatment with methanol. The vinylidene species 7 are deprotonated by NaOMe to produce the alkynyl compounds tripodCpL2RuC≡CR (9). Methylation of 9 with F3CSO3CH3 results in the vinylidene derivatives L' = C=C(Me)R (R = tBu, 7d; R = Ph, 7e), having two organic substituents at the terminal carbon centre. For all vinylidene compounds with two different substituents at their terminal carbon atom, hindered rotation of the single-faced vinylidene π-ligand about its Ru–C bond is observed. Analysis by ³¹P-NMR spectroscopic coalescence measurements as well as line-shape analyses reveals activation enthalpies of around 40 kJmol^–1 for this rotation, with small activation entropies of around ±10 Jmol^–1K^–1. Solid-state structures of nine compounds of the type [tripodCpL2RuL']⁺ⁿ (n = 0, 1) demonstrate the remarkable conformational rigidity of the tripodCpL2Ru template. They also show that the possible strain imposed by linking the Cp ligand and the two donor groups L in one and the same chelate scaffolding does not appear to impose a serious steric strain on these templates.

The preparation of novel dinucleating pyrazolate ligands H5L3- H5L8carrying chelating side arms with appending secondary amine functions is reported. Following different synthetic routes, either CH2CF3, C6H2F3, or C6F5moieties can be introduced as substituents at the terminal nitrogen atoms. These systems are reminiscent of two coupled coordination compartments of the potential triamidoamine-type. Crystallographic analyses of a series of bimetallic complexes of the CH2CF3-substituted ligand H5L4with NiCl2and CoCI2reveal manifold coordination modes in the solid state, resulting from the facile detachment of a single or several N-donor sites from the metal centers. Coordination number sets {4/6} (in H5L4Co2Cl4) and {5/6} (in H4L4Ni2Cl3, H4L4Co2Cl3and H5L4Ni2Cl4) are thus observed. In the non-deprotonated H5L-type systems the remaining protons are found to be scavenged by a pyrazolate-N (in H5L4Ni2Cl4) or an amine function of a ligand side arm (in H5L4Co2Cl4).

Dinuclear Co(III) complexes of the type [(triphos)Co(C6X2Z1Z2Z3Z4)Co(triphos)]2+(Z1-4= O, NR, S; R = H, Me; X = H, Cl, Br, I; 1- 62+) have been prepared and characterized by MS, IR, NMR, cyclovoltammetric and UV/VIS/NIR measurements and by X-ray analyses (12+, 3a2+and 42+). Their redox behaviour and the energy of their low energy LMCT bands was studied and compared to the properties of the mononuclear complexes [(triphos)Co(C6H4Z1Z2)]+(Z1-2= O, NH, S).

Salts with binuclear anions of the general formula [(η3-C3H4R)(CO)2Mo(μ-OR′)2(μ-OR″)-Mo(CO)2(η3-C3H4R)]-(R = h , R′, R″ = Me, 2 ; R = CH3, R′ = CH(CH3)2, R″ = OH, 3; R = CH3, R′ = OH, R″ = OSiMe3, 4) have been synthesised via reaction of [(η3-C3H4R)- Mo(CO)2(CH3CN)2(thf)]+BF4-, 1, with NaOMe, NaOiPr, and KOSiMe3. All products were characterised spectroscopically and investigated by single crystal X-ray analysis. In the case of 3 low temperature 2D-NMR spectra revealed that the solid state structure is maintained in solution and that the compound shows a trigonal twist-rearrangement at room temperature.

The tripod ligands RCH2C(CH2PPh2)3react with (CH3CN)6Fe(BF4)2to yield the tripod-Fe(II) complexes RCH2C(CH2PPh2)3Fe(CH3CN)3(BF4)2(R = H, la; R = Ph, lb). The octahedral low spin Fe(II) compounds are shown by cyclic voltammetry to undergo reversible one electron oxidation at +1.47 V (vs. SCE) to give the corresponding Fe(III) derivatives.

The synthesis of formaldehyde complexes (OC)2L2FeCH2O(L=P(OEt)3(2b), L = P(OiPr)3 (2c)) and CpRe(CO)2CH2O (3) is reported. A(OC)2[P(OMe)3]2FeCH2O compound (2a) reacts with CO,PPh3 and C2H4substituting the CH2O ligand. CH3I and H2also cause elimination of formaldehyde with oxidative addition to the Fe(CO)2[P(OMe)3]2fragment. HI adds to 2c to give a iodomethyl complex 5, which has been characterized by an X-ray structure determination.

Acetal complexes of the type (OC)5MnCH(XR)2, RX = PhO (1a), (RX)2= 1,2-dioxybenzene (1b), (RX), = S-(CH2)3-S (2) and (5) were synthesized. Glyoxyloyl acetal derivatives (OC)5MnC(O)CH(XR)2, RX = PhO (3a), (RX)2= 1,2-dioxybenzene (3b), (RX)2= S-(CH2)3-S (4) were obtained by the action of NaMn(CO)5upon the corresponding acid chlorides or anhydrides, la can be transformed to 3a by CO insertion, 1a has been characterized by an X-ray structure determination.

Phosphonomanganese complexes (CH3O)2(O)PMn(CO)3[P(OCH3)3]2(1b), (CH3O)2(O)PMn(CO)2[P(OCH3)3]3(1c) are obtained via demethylation of the corresponding cationic substituted carbonylmanganese compounds with KHB(secBu)3. The reaction of NaBH4in methanol with cationic phosphorus donor substituted carbonyl manganese compounds leads to formyl complexes (OC)3L2MnCHO (L = P(OCH3)3(3a), L = P(OEt)3(3c), L = P(OiPr)3(3d), L = PPh3(3e)) and (OC)2[P(OCH3)3]3MnCHO (3b). 3d decomposes thermally to give an (OC)3[P(OiPr)3]2MnH and an (OC)2[P(OiPr)3]3MnH complex. The latter has been characterized by an X-ray structure determination.

(nC3H7)As(CN)2(1) reacts with CO2(CO)8(2) to yield the cluster 3 in which two (nC3H7)As fragments are coordinated to Co(CO)n (n = 1, 2, 3) groups. The cluster 3 has been characterized