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Purpose The purpose of this paper is to understand the relationship between consumers and organic wine purchases and how this production process can affect their willingness to pay a premium price. The aim of this paper is, therefore, to assess the role of organic attributes on the consumer’s choice, and how consumer socio-demographic characteristics influence the premium price for organic wine. Design/methodology/approach This survey represents the continuation of a paper already published by the same authors, which was aimed at identifying the factors that influence the preference and consumption of wine. The information about wine consumers was collected by the use of an ad hoc questionnaire, administered near very busy places, (supermarkets, main squares, theatres, universities and municipal offices) in a random way, within several municipalities in the province of Messina (Italy). The questionnaire, which was anonymous, was distributed directly with the face-to-face method. In total, 1,097 subjects compose the obtained sample. Among these, 459 subjects (42%) said they consumed organic wine, while the remaining 638 (58%) said they did not consume it. In this research, the non-parametric combination test is used, based on a permutation test, chosen for the several optimal properties which characterize it. Permutation tests represent an effective solution for problems concerning the testing of multidimensional hypotheses that are difficult to face in a parametric context. Findings The results obtained may have interesting implications for wineries in the prediction and choice of the company to convert traditional production into organic production, to meet new markets and new segments of consumers. In this direction, without any doubt, organic wines represent an opportunity for the wineries. Research limitations/implications Although field experiments are extremely useful for testing behavioural hypotheses, they are often limited by the small sample. Originality/value The originality of the research lies mainly in a deeper knowledge of organic wine consumption trends. The study carried out highlights how important it is to know which factors restrain consumers from buying wine so that companies can review their promotion and communication policies and, if possible, meet the needs of the market. The strength of this paper is the use of an adequate statistical instrument. This multivariate and multistrata procedure allows us to reach effective solutions concerning problems of multidimensional hypotheses verifying within the non-parametric permutation inference; it is used in different application fields that deal with the verifying of multidimensional hypotheses with a complexity that cannot be managed in a parametric context.

The growing presence of Sicilian sustainable wine has pushed the research group to investigate and analyse the consumers' behaviour and their potential willingness to pay a premium price for the wine obtained through sustainable production processes. The analysis of the consumer's behaviour towards the wine made with sustainable production methods is carried out in order to provide potentially useful indications to Italian and in particular Sicilian wine enterprises regarding the production and marketing strategies to undertake in a future perspective. This study shows the result of an empirical investigation on the consumption of sustainable wine in Sicily. Through the Ordered (demographic profile, preference and attitudes), which influence the consumers' choices regarding sustainable wine. The assessment, based on the submission of a questionnaire, has highlighted the willingness to pay a premium price on the part of the 546 consumers interviewed. The study points out that the knowledge of sustainable production methods significantly influences the decision to support a premium price for wine consumption. This attests to the fact that a more attentive and informed consumer is ready to pay more for products obtained according to the principles of environmental sustainability. Keywords: Wine, Willingness to pay, Sustainability, Price

PurposeThe purpose of this paper is to attempt to outline the standard profile of the typical wine consumer, by identifying some relevant features that can influence his/her purchasing choices. Therefore, the purpose of the research is to identify the pre-eminent attributes for wine consumers and the different levels of importance that consumers ascribe to the attributes identified at the time of purchase.Design/methodology/approachIn order to collect the necessary data, an ad hoc questionnaire was utilized. The questionnaire, which was anonymous, was directly distributed with the face-to-face method. In total, 1,500 copies of the questionnaire had been prepared. The data collected were processed through the use of the binary logistic regression model and the ordinal logistic regression model. The first binary logistic regression model allows to evaluate the dependence of the dichotomous variable on some potential predictors. The ordinal logistic regression model, known in literature as a cumulative model of proportional quotas, is generally appropriate for situations in which the ordinal response variable has discrete categories.FindingsThe results returned by the elaboration of the binary logistic regression model refer to the influence of the variables sex, age, educational status and income on the “wine consumption” result, which is a dichotomous variable. The only variables found to be statistically significant are gender and educational status. The most significant variables that emerged from the implementation of the ordinary logistic regression model are gender, brand, choice based on price, place of production, harvest and certification. The analysis carried out has shown that with reference to wine as a product, it is essential to focus on several attributes, among which there are of course quality and brand.Research limitations/implicationsAlthough field experiments are extremely useful for testing behavioral hypotheses, they are often limited by a small sample. Future research in this area might focus on the knowledge level of sustainable wine of the consumer. In relation to the knowledge of the characteristics of the wine, it is possible to estimate the willingness to pay a surplus for a wine produced with sustainable methods by the consumer and the possible level of price premium.Originality/valueThe originality of the research lies mainly in a deeper knowledge of wine consumption trends. This information is useful to better define the wine market and to allow, especially to small businesses, to establish effective marketing strategies in relation to the real preferences of consumers and the decision-making process of choice put in place by them. In order to achieve this, the influence of all the variables on the “satisfaction of wine consumption” result was evaluated. The strength of this paper is the use of an adequate statistical approach based on the use of models, typical of inferential statistics, to reach conclusions that can be extended to the entire population of wine growers.

This engaging book attracts the reader’s attention from the very beginning. Niall Kishtainy writes with accessible language, dealing with his subject with great simplicity, with daily examples that...

Pain assessment in patients with disorders of consciousness (DoC) is a controversial issue for clinicians, who require tools and standardised procedures for testing nociception in non-communicative patients. The aims of the present study were, first, to analyse the psychometric properties of the Italian version of the Nociception Coma Scale and, second, to evaluate pressure pain thresholds in a group of patients with DoC. The authors conducted a multi-centre study on 40 healthy participants and 60 DoC patients enrolled from six hospitals in Italy. For each group an electronic algometer was used to apply all nociceptive pressure stimuli. Our results show that the Italian version of the NCS retains the good psychometric properties of the original version and is therefore suitable for standardised pain assessment in clinical practice. In our study, pressure pain thresholds measured in a group of patients in vegetative and minimally conscious state were relatively lower than pain threshold values found in a group of healthy participants. Such findings motivate additional investigation on possible pain sensitisation in patients with severe brain injury and multiple co-morbidities, and on application of tailored therapeutic approaches useful for pain management in patients unable verbally to communicate their feelings.

The paper looks at subjective well-being, defined in terms of individuals’ self-reported satisfaction with life, investigating nine dimensions (domains). The combination of the selected domains is ...

Cel – Celem badania jest analiza dynamiki gospodarczej i finansowej spoldzielni rolniczej w fazie początkowej. Metodologia – Badanie rozpoczyna sie od analizy alternatywnych form produktow marketingowych, ktore są niezbedne do określenia pola operacyjnego firmy. Finansowanie przedsiebiorstw spoldzielczych zawsze bylo niezwykle istotną kwestią w zarządzanie tego typu dzialalności. Istotnie, parametry techniczne i prawne tych firm mają ograniczone mozliwości do źrodel finansowania. Oryginalnośc/wartośc – W calej tej pracy, staraliśmy sie zaproponowac instrumenty finansowe, ktore najlepiej odpowiadają na potrzeby spoldzielni rolnej w fazie początkowej.

The paper reports the analysis of biomass derived from maintenance of a vineyard, to assess its potential as an alternative energy source, instead of the usual disposal of the wine supply chain’s residuals. The site studied is within the province of Messina, Sicily, in the area of Mamertino wine PDO, a wine of superior quality. The analysis suggests that use of this kind of biomass may allow a fossil fuel such as liquefied petroleum gas (LPG) to be replaced by a wine wood chip biomass boiler, thus meeting economic and environmental criteria by reason of recycling for sustainability.

After in-depth studies, the World Health Organization (WHO), asserts and suggests that in order to improve human health and well-being it is necessary to eat 400 grams of fruit and vegetables on a daily basis, as well as to consume potatoes and other starchy tubers such as manioc. In Europe, recommendations vary from country to country. Generally, these suggestions are in line with those of the WHO. However, some countries recommend a greater amount: For example, Denmark suggests more than 600 grams each day. The main goal of the present work is to analyse the fruit-consumption behaviour among young people, particularly university students and to identify the target of young people who frequently consume fruit. The present survey, therefore, has the aim of establishing a scientific reference framework regarding the propensity to “fruit” consumption in the diet of the students attending the University of Messina. In order to identify the existence of possible variables that may influence the frequency of fruit consumption, it was deemed appropriate to estimate an adequate regression model. Since the response variable was one of ordinal type on 4 levels (0 = never; 1 = once or twice a week; 2 = 3-5 times a week; 3 = each day) the Cumulative Proportional Odds Model, an extension of the general linear model to ordinal categorical data, was used.

Carrying out many intensive human activities in different areas including closed and semi-closed basins has consequences on long-medium term, with a strong environmental impact on the coastal and marine zone degradation. In many coastal regions these aspects - on the long term - caused rapid alterations and severely influenced the sustainability of the coastal ecosystems. Urbanization, mainly produced by tourist activities, causes an increase of the overcrowding costs. It is important to observe that the relation between tourism and environment is not immediate, but it is connected, both to the changes of the production processes of tourist services, and to the changes of residents and of the tourists consumptions. If the direction of these effects is the same, an economic growth based on tourism will have positive effects. Therefore, the flows of tourists along the coasts have an important impact on the ecosystem and an approach based on the Kuznets’s Curve would allow us to highlight the relation between the cost of the environmental degradation (environmental damage or as lack of monetary incomes) and the advantages of the economic growth.

Purpose The purpose of this paper is to report a survey in random-selected supermarkets in Italy in order to identify the attitudes and perceptions of consumers toward milk and in particular toward donkey milk. Design/methodology/approach The analysis was conducted through Google Forms platform of docs.google interviews with a sample of 705 consumers who were given a questionnaire to collect information about their economic status and their attitudes toward milk and special milk consumption. Findings The results were analyzed in order to identify the socio-economic and behavioral characteristics of homogeneous groups of consumers. They consume milk mainly because it is not expensive and it is possible to easily buy it in the supermarket. They consume special milk mainly because of food allergies or intolerances. They would like to buy special milk at large-scale retail trade outlets; they underline difficulties in finding and purchasing it. They think that the price of special milk is very high. Originality/value The results showed that those who occasionally consume special milk choose it because it is more nourishing or for health reasons; there is also a significant association between the judgment on prices of special milk and the frequency of purchase. The estimation of a generalized linear model allowed to highlight that only age and the presence of health problems/intolerances are significant predictors of special milk consumption.

The paper analyzes the biomass resulting from the processing of olive oil, in order to evaluate, in terms of economic sustainability, its importance in energy processes and the use of alternative paths other than the normal disposal process of the residues of the oil industry productive chain. Attention has been focused on the manufacturer of “Valdemone DOP” extra virgin olive oil, located in Sicily (Italy), in order to evaluate the possible energy recovery, directly by the farmer, of by-products of the production chain of olive oil, in order to make the whole process more efficient, using the scraps from the mill directly on site. The economic analysis aims at identifying measures for energy recovery from by-products; in order to reduce the incidence of the cost of waste disposal on the cost of the production of the oil; to energy conservation through the use of by-products as renewable fuel.

PurposeIn the food chain the identification of household food wastes represents the most problematic aspect to analyze: both as regards the assessment of its qualitative and quantitative aspects and for the detection of measures to reduce or control its generation. In 2012, in fact, the analyzed area showed an inequality index for disposable income of 6.3, and a relative poverty risk index of 42.3. The paper aims to discuss these issues.Design/methodology/approachIn order to get deeper insights into consumers’ wasting behaviors, a survey on food waste generation in households was carried out in a province of Sicily (Italy). The questionnaire has been formulated taking into account the socio-demographic characteristics for the person who, in the family, usually makes the expenditure, in particular: gender, age, marital status, number of household members, education level, type (single, with or without children, married with or without children), worker and/or student if responsible for food shopping, the number of monthly meals, the kind of ready meal eaten (frozen, fresh, canned or freeze-dried), net monthly income for the family, etc. (adapted by Baeet al., 2010). The data collected from the statistical return of the consumers were drawn up to transform the same data into information of simpler and more concise interpretation.FindingsThe results of the survey are presented in this paper. They can help understand the reasons for discarding edible food and to identify the food groups that are most wasted.Research limitations/implicationsThe analysis of a larger land area or community allows most relevant conclusions. The research has an exploratory perspective since the sample strategy is not probabilistic.Social implicationsThe findings could be susceptible to support practical and social implications for the identification of measures and instruments aimed at reducing food waste and at increasing consumers’ awareness on that issue.Originality/valueThe study can stimulate sustainable consumption and consumer behavior especially in light of the current economic crisis.

The purpose of the present survey is to study and to investigate the proper eating style, focusing the attention on the propensity to “egg” consumption, in the diet of young people, with reference to the students attending the University of Messina. The data collection technique that was used consisted of the administration of a distributed anonymous ad hoc questionnaire by directly interviewing a sample of university students. In order to individualize the possible variables which may influence the frequency of egg consumption, a logistic regression model was used. It is a particular case of generalized linear model whose link function is the log it function. It is frequently applied when the dependent variable y is, dichotomous. The research results indicate that the only two statistically significant variables are the eating style and the reading of the product label. Moreover, the Hosmer and Leme show test for model’s adequacy guaranteed that the estimates provided by the model are not significantly different from the observations.

The survey on consumption of wine has been conducted in the period between April 20th and July 10th of 2011 on a sample of 200 consumers of Sicily. The recognition by the administration of the product was mainly conducted at some outlets, supermarkets, wine shops and bars, interviewing a sample of consumers directly with the method "face to face." The survey purpose was conducted to understand the needs of wine consumers and the role played by the mark of quality in the choice of purchase, and finally the degree of appreciation and consumption of Sicilian wine.

The survey on consumption of wine has been conducted in the period between April 20th and July 10th of 2011 on a sample of 200 consumers of Sicily. The recognition by the administration of the product was mainly conducted at some outlets, supermarkets, wine shops and bars, interviewing a sample of consumers directly with the method "face to face." The survey purpose was conducted to understand the needs of wine consumers and the role played by the mark of quality in the choice of purchase, and finally the degree of appreciation and consumption of Sicilian wine.

The EU boasts an important agrifood quality heritage that is often famous only in local scope. This can potentially represent an opportunity in more for the primary sector, through the valorisation and promotion policy, the production can be introduced on various markets, or still better be made known to the tourist-consumer that travels to the discovery of new knowledge and tastes. This singular type of tourism represents the exaltation of the sustainable interaction between environment and agrifood. The fulcrum of the enogastronomic tourism is the top level of the quality of local products. This potential still untapped linked to the tourism of the food, can contribute to develop the economy of the rural areas also in the East Countries, where the agriculture has an important role in the socioeconomic woven of these countries and where the future programming of the politics of rural development will assign to resources financial institutions in order to favour the synergies’ development between agricultural and tourism. An example of this logon and integration between agriculture and tourism is represented by the thematic routes of the taste and more in particular from the wine roads. The paper wants to underline the importance that the tourism linked to food and wine, and in particular the Wine Route, can play in enhancing the rural area triggering a series of economic-productive processes that revitalize the local neglected economy from the process of globalization in existence from various years In fact the farms that join to a themed tourist route can exploit this important instrument of communication in order to introduce to the tourist-consumers own local typical productions. Every year the enogastronomic tourism records trend of ever increasing tourist flows, then becomes strategic to know, anticipating, the requirements manifested from the wine tourist. For this reason the paper it is concluded with the construction of an identikit of the wine tourist looking for to interpret its behaviours, tastes and preferences that are manifested the choice of tourist destination at the completion of the holiday.

Tourism has represented one of the major sources of balance of trade earnings for many years in the most developed countries. According to estimates by the World Tourism Organization (WTO), world tourism flows will grow by 4-5% annually over the coming years, reaching in 2020 an estimated number of 1.6 billion international arrivals, of which 378 million will be short haul international travellers. With the passage of time demand will become more diversified and this will lead to the spread of “new tourism”, the search for new products and increasingly diverse offers, characterized by organized local tourist systems.This paper underlines the importance of the tourist district model as a strategic tool for creating innovative processes of endogenous development in a highly globalized framework, moreover it tries to highlight the peculiarities of tourist districts and their importance in overcoming the major limitations of the distribution chain. Therefore, the birth of the tourism district represents an important opportunity for the promotion of tourism development of different local realities.

Herein, we describe the synthesis of N,N′,S donor ligands 2-(1-(3,5-diisopropyl-1H-pyrazol-1-yl)-3-(methythio)propyl)-4-methoxy-3,5-dimethylpyridine (L1) and 2-(1-(3,5-diisopropyl-1H-pyrazol-1-yl)-2-(methythio)ethyl)-4-methoxy-3,5-dimethylpyridine (L2). Cu(I) complexes were prepared by reacting L1 or L2 with [Cu(CH3CN)4]BF4 or CuCl. The coordination behavior of the thioether arm of the ligands was found to determine the nuclearity of the resulting complexes, in which [Cu(L1)PPh3]BF4 (1) is polynuclear, [Cu(L2)PPh3]BF4 (2) is mononuclear, while [Cu(L1)]2(BF4)2 (3), [Cu(L2)CH3CN]2(BF4)2 (4), and [Cu(L1)Cl]2 (5) are dinuclear. In the dimeric complex [Cu(L2)Cl]2 (6), the sulfur atoms are not metal-bound. Rather, the two bridging chloride ions link the two copper centers. Compounds 4–6 are luminescent in the solid state, and exhibit emission bands centered at 490 nm (4), 544 nm (5), and 562 nm (6), respectively. Their excitation spectra display bands at 280 nm and 380 nm. According to DFT calculations, the HOMO is distributed partially over the metal centers and partially over the chloride anions (5 and 6) or the sulfur atoms (4) of the ligands, while the LUMO is a π∗ antibonding pyridine orbital. This suggests that the emission properties are derived from metal-to-ligand charge-transfer (MLCT), halide-to-ligand charge-transfer (XLCT), and ligand-to-ligand charge-transfer (LLCT) excited states.

The N,N',S-donor ligand 4-methoxy-3,5-dimethyl-2-((3-(2-(methylthio)phenyl)-1H-pyrazol-1-yl)methyl)pyridine (L) was prepared from 2-(chloromethyl)-4-methoxy-3,5-dimethylpyridine hydrochloride and 3-(2-(methylthio)phenyl)-1H-pyrazole. The Cu(I) complexes [Cu2(L)2CH3CN][Cu(L)CH3CN](BF4)3 (1), [Cu(L)PPh3]BF4 (2), and [Cu6(L)2(C6F5S)6] (3) were prepared and characterized by X-ray crystallography (PPh3=triphenylphosphine, C6F5S-=pentafluorothiophenolate). The unit cell of compound 1 consists of cocrystallized mononuclear and dinuclear entities in which all of the copper atoms exhibit distorted tetrahedral coordination. Compound 2 is monomeric with L bound in the kappa3-N,N',S mode and a PPh3 molecule that completes the coordination environment. Compound 2 presents a fluxional behavior in CDCl3 solution due to the boat inversion of the six-membered N,N' chelate ring (DeltaH=+43.6(3) kJ mol(-1), DeltaS=-16(1) J mol(-1) K(-1)). Crystallization of 3 in acetonitrile leads to a polynuclear structure that contains a CH3CN molecule coordinated to one of the copper atoms: [Cu6(L)2(C6F5S)6CH3CN] (3a). The core of 3a partially resembles a {Cu4S6} adamantane-like moiety, the only difference being that the Cu-NCCH3 interaction leads to the opening of the cluster by disrupting a Cu-Cu interaction. Part of this assembly is found in the yeast metallothionein copper(I)-cysteinate core whose crystal structure has recently been reported. Two additional [Cu(L)]+ peripheral moieties interact with the cluster by means of bridging thiolates. ESI-mass spectrometry, conductivity measurements, and 1H/19F pulsed gradient spin echo (PGSE) NMR experiments suggest that 3a dissociates in acetonitrile solution: 3a+CH3CN-->[Cu4(C6F5S)6]2-+2[Cu(L)CH3CN]+. The stability of the cluster with respect to the hypothetical mononuclear species, [Cu(L)(C6F5S)], is confirmed by DFT calculations (B3LYP), which illustrate the exergonic character of the reaction: 6[Cu(L')(C6H5S)]-->[Cu6(L')2(C6H5S)6]+4L' (DeltaG298=-58.6 kJ mol(-1), where L' and C6H5S- are simplified models for L and C6F5S-, respectively). The energetics pertinent to the ionic dissociation of the cluster in acetonitrile is computed using the polarizable continuum model (PCM) approach.

The reactions of the triply bonded anion [Mo2Cp2(μ-PCy2)(μ-CO)2]- (Li+ salt) with [NH4]PF6, MeI, and PhCH2Cl give, with good yields, the corresponding hydride- or alkyl-bridged derivatives [Mo2Cp2(μ-X)(μ-PCy2)(CO)2] (X = H, Me, CH2Ph). The related phenyl complex [Mo2Cp2(μ-Ph)(μ-PCy2)(CO)2] can be obtained upon reaction of the above anion with Ph3PbCl. According to the corresponding X-ray diffraction studies, the latter complex displays its phenyl group bonded to the dimetal center exclusively through the ipso carbon atom, while the methyl and benzyl complexes adopt an asymmetric α-agostic structure whereby one of the C−H bonds of the bridgehead carbon is bound to one of the molybdenum atoms. The intermetallic distances remain quite short in all cases, 2.56−2.58 A. In solution, the hydride complex exhibits dynamic behavior involving mutual exchange of the carbonyl ligands. The alkyl derivatives behave similarly to each other in solution and also exhibit dynamic behavior, possibly implying the presence of s...

The 30-electron hydride complex [Mo2Cp2(μ-H)(μ-PCy2)(CO)2] reacts at room temperature with p-tolylacetylene to give the unsaturated σ:π-bonded alkenyl derivatives trans-[Mo2Cp2(μ-η1:η2-CRCH2)(μ-PCy2)(CO)2] and trans-[Mo2Cp2(μ-η1:η2-CHCHR)(μ-PCy2)(CO)2] (R = ptol; Cp = η5-C5H5), with the α-substituted alkenyl complex being transformed completely into its β-substituted isomer slowly at room temperature. In solution, both compounds exhibit an isomeric equilibrium (rapid on the NMR time scale) involving the alternate π-binding of the alkenyl ligand to each of the metal centers. In addition, the presence of CO allows the partial conversion of the α-substituted complex into its cis-dicarbonyl isomer cis-[Mo2Cp2(μ-η1:η2-CRCH2)(μ-PCy2)(CO)2], so as to reach a roughly equimolar equilibrium ratio. In contrast, the β-substituted alkenyl complex experiences full carbonylation under the same conditions to give the tricarbonyl complex [Mo2Cp2{μ-η1:η2-CHCHR}(μ-PCy2)(CO)3], but similarly displaying a cisoid arrangement o...

The growing importance of Sicilian wines in the Italian market provides the context in which this paper is set. This study presents the results of a recent survey on Sicilian wine consumption in Italy. By means of a binary response model, this paper evaluates the main determinants (demographic profile, preference and attitudes) that influence Italian consumers’ preferences for Sicilian wines. The estimates, based on the stated preference of 953 Italian wine consumers, emphasize that income and habits to purchase at wine shops and the habit to drink between meals significantly influence the willingness to consume Sicilian wines. Furthermore the sample propensity to consume the Sicilian wine increases for white wines and when the consumption takes placed in public spaces.

A0, a Cu(II) thioxotriazole complex, produces severe cytotoxic effects on HT1080 human fibrosarcoma cells with a potency comparable to that exhibited by cisplatin. A0 induced a characteristic series of changes, hallmarked by the formation of eosin- and Sudan Black-B-negative vacuoles. No evidence of nuclear fragmentation or caspase-3 activation was detected in cells treated with A0 which, rather, inhibited cisplatin-stimulated caspase-3 activity. Membrane functional integrity, assessed with calcein and propidium iodide, was spared until the late stages of the death process induced by the copper complex. Vacuoles were negative to the autophagy marker monodansylcadaverine and their formation was not blocked by 3-methyladenine, an inhibitor of autophagic processes. Negativity to the extracellular marker pyranine excluded vacuole derivation from the extracellular fluid. Ultrastructural analysis indicated that A0 caused the appearance of many electronlight cytoplasmic vesicles, possibly related to the endoplasmic reticulum, which progressively enlarge and coalesce to form large vacuolar structures that eventually fill the cytoplasm. It is concluded that A0 triggers a non-apoptotic, type 3B programmed cell death (Clarke in Anat Embryol (Berl) 181:195-213, 1990), characterized by an extensive cytoplasmic vacuolization. This peculiar cytotoxicity pattern may render the employment of A0 to be of particular interest in apoptosis-resistant cell models.

Complexes [PPh3Cu(Tr(Mes,Me))] (1), [PPh3Cu(Tr(Me,o-Py))] (2), and [PPh3Cu(Br(Mes)pz(o-Py))] (3) (Tr(Mes,Me) = hydrotris[1,4-dihydro-3-methyl-4-mesityl-5-thioxo-1,2,4-triazolyl]borate; Tr(Me,o-Py) = hydrotris[1,4-dihydro-4-methyl-3-(2-pyridyl)-5-thioxo-1,2,4-triazolyl]borate; Br(Mes)pz(o-Py) = hydro[bis(thioxotriazolyl)-3-(2-pyridyl)pyrazolyl]borate; PPh3 = triphenylphosphine) were synthesized by the reaction of dinuclear complexes [Cu(Tr(Mes,Me))]2, [Cu(Tr(Me,o-Py))]2, [Cu(Br(Mes)pz(o-Py))]2, and PPh3. 1-3 were characterized by 1H, 13C, and 31P NMR spectroscopy and ESI-mass spectrometry. Crystal structure analyses were performed for 1 and 2. Both complexes crystallize in the triclinic P space group with the metal in a slightly distorted tetrahedral geometry (S3P coordination) bound by a kappa3-S3 ligand and a PPh3 molecule. The solution molecular structures were investigated by means of variable-temperature (210-310 K, CDCl3, 1-2; 200-310 K, CD2Cl2, 3) and NOESY NMR spectroscopy. The solution structures of 1-2 are in accordance with the X-ray structures, and the complexes do not exhibit fluxional behavior. On the other hand, 3 is subject to an equilibrium between two species with a coalescing temperature of approximately 260 K. DFT geometry optimizations suggest that the major species of 3 consists of the Br(Mes)pz(o-Py) ligand bound to Cu(I) in the kappa3-S2H fashion with two C=S groups and a [Cu...H-B] interaction. A PPh3 completes the copper coordination (S2HP coordination). The complex [TuCu(Tr(Mes,Me))] (4) (Tu = thiourea) was crystallized using an excess of Tu with respect to [Cu(Tr(Me,2-Py))]2 (approximately a 6:1 ratio). The metal adopts a distorted tetrahedral geometry with an overall S3H coordination determined by the bound kappa3-S2H ligand (two C=S groups and a [B-H...Cu] interaction) and by a Tu. The reactivity of dinuclear complexes [Cu(Tr(Mes,Me))]2, [Cu(Tr(Me,o-Py))]2, and [Cu(Br(Mes)pz(o-Py))]2 with monodentate ligands was investigated by means of NMR titrations with PPh3, Tu. and pyridine (Py), and formation constants for the adducts [DCu(L)] (D = monodentate donor, L = tripodal ligand) were determined.

Reaction of Na2[Mn2{μ-OP(OEt)2}{μ-P(OEt)2}(CO)6] with SnR2Cl2 (R = Bu, Ph) in tetrahydrofuran leads finally to the stannyl-bridged heptacarbonyl compounds [Mn2{μ-Sn:Sn,P-SnR2OP(OEt)2}{μ-P(OEt)2}(CO...

Dinuclear Cu(I) complexes with bifunctionalized homoscorpionate ligands, hydrotris(thioxotriazolyl)borato [Li(Tr(Me,o)(-)(Py)) (1) and Li(Tr(Mes,Me)) (2)], and the heteroscorpionate ligand hydro[bis(thioxotriazolyl)-3-(2-pyridyl)pyrazolyl]borato [K(Br(Mes)pz(o)(-)(Py))] (3) were synthesized and crystallographically characterized. The complexes [Cu(Tr(Mes,Me))](2) (4) and [Cu(Tr(Me,o)(-)(Py))](2) (5) exhibit a similar coordination geometry where every metal is surrounded by three thioxo groups in a trigonal arrangement. The presence of a [B-H...Cu] three-center-two-electron interaction in both compounds causes the overall coordination to become tetrahedrally distorted (S(3)H coordination for each metal). The complex [Cu(Br(Mes)pz(o)(-)(Py))](2) (6) presents a trigonal geometry in which the metals interact with two thioxo groups and a bridging pyrazolyl nitrogen atom. A weak contact with a pyridine nitrogen atom completes the coordination of the metals (S(2)N,N' coordination for each metal). [Cu(Tr(Mes,Me))](2), [Cu(Tr(Me,o)(-)(Py))](2), and [Cu(Br(Mes)pz(o)(-)(Py))](2) exhibit fluxional behavior in solution as evidenced by variable-temperature NMR spectroscopy, and for 5 and 6 two species in equilibrium [in the ratio 2/1 for 5 (CDCl(3)) and 3/2 for 6 (CD(2)Cl(2))] are distinguishable in the (1)H NMR spectra at 270 K. 2D-NOESY spectra recorded at 270 K assisted in the attribution of solution molecular geometries for each isomer of 5 and 6. The free energy of activation (DeltaG()(Tc)) was determined for both equilibria from the evaluation of the coalescence temperature. DFT calculations were performed to describe plausible molecular geometry for the minor isomer of 5 and 6 and to propose a possible mechanism of interconversion between major and minor isomers. Cyclic voltammograms were recorded in CH(2)Cl(2) (3 and 6) or CH(2)Cl(2)/CH(3)CN (1/1, v/v) (2, 4, and 5) solutions using 0.1 M TBAHFP or TBAOTf as supporting electrolytes. [Cu(Tr(Mes,Me))](2), [Cu(Tr(Me,o)(-)(Py))](2), and [Cu(Br(Mes)pz(o)(-)(Py))](2) exhibit a quasi-reversible Cu(I)/Cu(II) redox behavior with E(pa) = +719 mV and E(pc) = +538 mV for 4, E(pa) = +636 mV and E(pc) = -316 mV for 5, and E(pa) = +418 mV and E(pc) = -319 mV for 6.

Two new sulfurated triazoline ligands have been synthesized by functionalization of glycine and l -alanine (HL1 and HL2, respectively) at the carboxylate site with retention of chirality in the latter case. The ligands and their copper(II) complexes have been characterized by spectroscopic methods and their structures were determined by X-ray diffraction. The compound [Cu(H2L2)2](H5O2)(SO4)2(HSO4) presents a very disordered structure with regard to the anionic counterion and a very unusual elongated crystal cell. In all the complexes the ligands are (N,S) coordinated to copper(II), while the amino groups remain protonated and uncoordinated. The ligands have also been studied in solution and their dissociation constants were determined both by potentiometry and 1H NMR titrations. Potentiometric studies on the complex [Cu(H2L2)2](H5O2)(SO4)2(HSO4) were performed to determine the dissociation constants of the ligand once coordinated to the metal. The complex [CuCl2(H2L1)]Cl was studied also by magnetic susceptibility measurements, showing an interesting antiferromagnetic behavior at low temperature which has been interpreted on the basis of its crystal packing.

The complex [Ni(TrMe,o-Py)2] (2) {TrMe,o-Py=hydrotris[1,4-dihydro-4-methyl-3-(2-pyridyl)-5-thioxo-1,2,4-triazolyl]borate} was synthesized and characterized by UV–Vis spectroscopy, ESI-mass spectrometry and X-ray crystallography. Complex 2 crystallizes in the tetragonal I-42d space group. The metal presents a slightly distorted octahedral geometry (N4S2 co-ordination) bound by two ligands that behave in the S,N/N′ co-ordination mode: one of the three arms of each tripod is bound to the metal with the thioxo group, the second chelates N/N′ with the triazoline and pyridine nitrogen atoms and the third does not participate in the metal co-ordination. Ni/TrMe,o-Py complexation was studied by collecting visible spectra of 16 batch samples (10 ml) containing a fixed concentration of metal (9.994 × 10−4 mol dm−3) with increasing concentrations of ligand up to Ni/L=1/3 (L=TrMe,o-Py). For a Ni/L ratio of 1/2, ≈38% of NiL+ and ≈56% of NiL2 are present with respect to the total Ni(II) concentration. Conductivity (ΛM range 112–55 ohm−1 cm2 mole−1 in acetonitrile and ΛM range 15–8 ohm−1 cm2 mole−1 in DMF) and ESI-mass spectrometry results are consistent with a partial dissociation of 2 in acetonitrile and DMF solutions according to the equilibrium NiL2=NiL+ + L− in agreement with the spectrophotometric titration results. Cyclic voltammetry performed on acetonitrile solutions of 2 reveals the electrochemical activity of the TrMe,o-Py ligand, which undergoes irreversible oxidation and reduction processes at potential > +0.7 and ∼0 V, respectively. The occurrence of the Ni(II)/Ni(III) and Ni(II)/Ni(I) electrochemical events could not be determined.

Reaction of the unsaturated dihydride [Mn2(μ-H)2(CO)6(μ-dppm)] with Li[BHEt3] proceeds stepwise, giving first the anionic hydride [Mn2(μ-H)(CO)6(μ-dppm)]- and then the dianion [Mn2(CO)6(μ-dppm)]2-,...

Preparations of copper(I) and bismuth(III) complexes of hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate (Tr(Et,Me)) are described. These complexes have been characterized by means of spectroscopy and microanalysis. Molecular structures of [Cu(Tr(Et,Me))](2) x 2.5CH(3)CN x 0.5H(2)O (3a) and [Bi(Tr(Et,Me))(2)]NO(3) x 2CHCl(3) (4a) have been determined by single-crystal X-ray diffraction. In the centrosymmetric dimeric copper(I) complex, Tr(Et,Me) acts in the k(3)S,S',H:kS' ' coordination mode. The metal is found in a distorted trigonal geometry as the ligand exhibits an "S(3)-inverted" conformation at the boron center so that a weak [B-H.Cu] agostic interaction renders the overall coordination of the (3 + 1) type. On the other hand, in the bismuth complex, Tr(Et,Me) presents the k(3)S,S',S' ' coordination mode and the "S(3)-normal" conformation. The metal is found in a regular octahedral geometry bound by six thioxo groups of two ligands. Species distributions in solution have been studied using electrospray ionization mass spectrometry upon dissolution of 3a and 4a crystals in acetonitrile. Monomeric and polynuclear copper(I) complexes with different M:L ratios are present in solution, while for 4a only the monomeric species is present.