Table grapes are food products of considerable commercial value for several countries (USA, Brazil, Italy, South Africa, China, Chile, India and Australia are the most important producers). In Europe, Italy ranks first place for table grape production with more than eight million tons per year (ISTAT, 2011). Recently, we developed an innovative analytical method for the characterization of various table grape cultivars. In our study, multivariate statistical analysis applied to 1H NMR data of table grapes, revealed that the inter-vineyard variability of the metabolic profile has a greater discriminating effect over the intra-vineyard one.1 This presentation deals with the effects of several agronomical practices on the metabolic profile of the table grapes during different production stages. The variation of the metabolic features of the grapes was followed by 1H NMR spectroscopy. Moreover, 1H NMR spectra of ripe table grapes were processed to be used as input for expert classification systems based on three different algorithms: J48, Random Forest and an Artificial Neural Network performed with the Error Back Propagation procedure. The performances of the three algorithms in the discrimination of grapes on the bases of some common features (variety, vintage, use of plant growth regulators, trunk girdling, vineyard location) will be shown. References: 1. V. Gallo, P. Mastrorilli, I. Cafagna, G. I. Nitti, M. Latronico, V. A. Romito, A. P. Minoja, C. Napoli, F. Longobardi, H. Schäfer, B. Schütz, M. Spraul, J. Agric. Food Chem. (2012), submitted.

Table grapes classification is an important task in the global market because of the interest of consumers to quality of foodstuff. Objective: an expert and innovative tool, based on several robust classifiers, was designed and implemented to achieve unequivocal criteria and support decision for the discrimination of table grapes. Materials: data are acquired by powerful analytical techniques such as Nuclear Magnetic Resonance (NMR) and are related to 5 attributes: production year, vineyard location, variety, use of plant growth regulators (PGRs) and application of trunk girdling. In particular, datasets consisting of 813 samples regarded the former 3 attributes while datasets based on 596 samples regarded the latter 2 ones. Methods: in absence of an a-priori knowledge, we addressed the problem as an inferential task and then adopted supervised approaches like error back propagation neural networks, trees and random forest classifiers able to manage information from training sets. Experimental Results and Conclusion: our study has shown that the three classifiers, especially that based on a supervised neural network, when applied to NMR data, give from good to excellent performances, depending on the attribute. Such performances pave the way to development of innovative tools for classification of table grapes.

‘Crimson Seedless’ is a table grape cultivar that often fails to develop adequate red color in Mediterranean climates. Application of abscisic acid (S-ABA) may be an aid for improving color, but its potential effects both on the overall quality and S-ABA concentration of the berry should be also considered. We tested two concentrations (200 and 400 mg/L) and different times of application (from one week after veraison up to nine days before harvest) of a commercial formulation of S-ABA (ProTone) in order to verify the effect on harvestable bunches, color, chemical characteristics, metabolic profile and S-ABA concentration in the berry. It was found that either the application of S-ABA at 400 mg/L one week after veraison or the application of S-ABA at 400 mg/L one week and four weeks after veraison positively affected the berry skin color shifting the hue (h◦) from 20 to a more red-violet hue (h◦=11-12). In general, the application of S-ABA, with the exception of the late treatments, enhanced coloration of the berries and increased the amount of harvestable bunches at the first pick because promoted the skin coloring process. S-ABA did not affect the berry firmness but reduced the berry detachment force. Nevertheless, the values remained sufficiently high and the general quality of the bunch was not compromised. Ripening parameters (°Brix, pH, titratable acidity) were not affected by S-ABA applications and even the primary metabolites profile was not influenced by the treatments, as ascertained by multivariate statistical analyses [Principal Component Analyses (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA)] applied to Nuclear Magnetic Resonance (NMR) data. The S-ABA concentration in the berry, when treatments were performed around veraison, was within the natural range for grape (10-400 ng/g f.w.), whereas when late treatments were applied (few days before harvest) the concentration was higher (more than 1000 ng/g f.w.). The best results for yield, quality and S-ABA concentration in the berry were observed for the treatments performed few days after veraison at the dose of 400 mg/L. This study gives new information about the positive effects of S-ABA on color with not particular change in the metabolic profile of the berry.

The reaction of [NBu4][(C6F5)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(O,O-acac)] (48 VEC) with [HPPh3][ClO4] gives the 46 VEC unsaturated [(C6F5)2Pt1(μ-PPh2)2Pt2(μ- PPh2)2Pt3(PPh3)](Pt2–Pt3) (1), a trinuclear compound endowed with a Pt-Pt bond. This compound displays amphiphilic behaviour and reacts easily with nucleophiles L yielding the saturated complexes [(C6F5)2PtII(μ-PPh2)2PtII(μ-PPh2)2PtII(PPh3)L] (L = PPh3 2, py 3). The reaction with the electrophile [Ag(OClO3)PPh3] affords the adduct 1·AgPPh3 that evolves, even at low temperature, to a mixture in which [(C6F5)2PtIII(μ- PPh2)2PtIII(μ-PPh2)2PtII(PPh3)2]2+(PtIII–PtIII) and 2 (plus silver metal) are present. The nucleophilic nature of 1 is also demonstrated through its reaction with cis- [Pt(C6F5)2(thf)2] which results in the formation of [Pt4(μ-PPh2)4(C6F5)4(PPh3)], 4. The structure and NMR features indicate that 1 can be better considered as a Pt(II),Pt(III),Pt(I) complex instead of a Pt(II),Pt(II),Pt(II) derivative. Theoretical calculations (DFT) on similar model compounds are in agreement with the assigned oxidation states of the metal centers. The strong intermetallic interactions resulting in a Pt2-Pt3 metal-metal bond and the respective bonding mechanism were verified employing a multitude of computational techniques (NBO analysis, the Laplacian of the electron density and the Localized Orbital Locator (LOL) profiles).

X-ray powder diffraction was combined, for the first time, with Nuclear Magnetic Resonance spectroscopy and direct infusion mass spectrometry to characterise fresh and brined grape leaves. Covariance analysis of data generated by the three techniques was performed with the aim to correlate information deriving from the solid part with those obtained for soluble metabolites. The results obtained indicate that crystalline components can be correlated to the metabolites contained in the grape leaves, paving the way to the use of X-ray diffraction analysis for food fingerprinting purposes. Moreover it was ascertained that, differently from most of the metabolites present in the fresh vine leaves, linolenic acid (an omega-3-fatty acid) and quercetin-3-O-glucuronide (a polyphenol metabolite) do not undergo sensible degradation during the brining process, which is used as preservative method for the grape leaves.

The dinuclear anionic complexes [NBu4]- [(RF)2MII(μ-PPh2)2M′II(N∧O)] (RF = C6F5. N∧O = 8-hydroxyquinolinate, hq; M = M′ = Pt 1; Pd 2; M = Pt, M′ = Pd, 3. N∧O = o-picolinate, pic; M = Pt, M′ = Pt, 4; Pd, 5) are synthesized from the tetranuclear [NBu4]2[{(RF)2Pt(μ-PPh2)2M(μ-Cl)}2] by the elimination of the bridging Cl as AgCl in acetone, and coordination of the corresponding N,O-donor ligand (1, 4, and 5) or connecting the fragments “cis-[(RF)2M(μ-PPh2)2]2−” and “M′(N∧O)” (2 and 3). The electrochemical oxidation of the anionic complexes 1−5 occurring under HRMS(+) conditions gave the cations [(RF)2M- (μ-PPh2)2M′(N∧O)]+, presumably endowed with a M(III),M′(III) core. The oxidative addition of I2 to the 8-hydroxyquinolinate complexes 1−3 triggers a reductive coupling between a PPh2 bridging ligand and the N,O-donor chelate ligand with formation of a P−O bond and ends up in complexes of platinum(II) or palladium(II) of formula [(RF)2MII(μ-I)(μ-PPh2)M′II(P,N-PPh2hq)], M = M′ = Pt 7, Pd 8; M = Pt, M′ = Pd, 9. Complexes 7−9 show a new Ph2P-OC9H6N (Ph2P-hq) ligand bonded to the metal center in a P,N-chelate mode. Analogously, the addition of I2 to solutions of the o-picolinate complexes 4 and 5 causes the reductive coupling between a PPh2 bridging ligand and the starting N,O-donor chelate ligand with formation of a P−O bond, forming Ph2P-OC6H4NO (Ph2P-pic). In these cases, the isolated derivatives [NBu4][(Ph2P-pic)(RF)PtII(μ-I)(μ-PPh2)MII(RF)I] (M = Pt 10, Pd 11) are anionic, as a consequence of the coordination of the resulting new phosphane ligand (Ph2P-pic) as monodentate P-donor, and a terminal iodo group to the M atom. The oxidative addition of I2 to [NBu4][(RF)2PtII(μ-PPh2)2PtII(acac)] (6) (acac = acetylacetonate) also results in a reductive coupling between the diphenylphosphanido and the acetylacetonate ligand with formation of a P−O bond and synthesis of the complex [NBu4][(RF)2PtII(μ-I)(μ-PPh2)PtII(Ph2P-acac)I] (12). The transformations of the starting complexes into the products containing the P−O ligands passes through mixed valence M(II),M′(IV) intermediates which were detected, for M = M′ = Pt, by spectroscopic and spectrometric measurements.

X-ray powder diffraction was combined, for the first time, with Nuclear Magnetic Resonance spectroscopy and direct infusion mass spectrometry to characterise fresh and brined grape leaves. Covariance analysis of data generated by the three techniques was performed with the aim to correlate information deriving from the solid part with those obtained for soluble metabolites. The results obtained indicate that crystalline components can be correlated to the metabolites contained in the grape leaves, paving the way to the use of X-ray diffraction analysis for food fingerprinting purposes. Moreover it was ascertained that, differently from most of the metabolites present in the fresh vine leaves, linolenic acid (an omega-3-fatty acid) and quercetin-3-O-glucuronide (a polyphenol metabolite) do not undergo sensible degradation during the brining process, which is used as preservative method for the grape leaves. (C) 2013 Elsevier Ltd. All rights reserved.

The reactivity of the complexes [PtCl2{Ph2PN(R)PPh2-P,P}] (R = −H, 3; R = −(CH2)9CH3, 8) toward group 6 carbonylmetalates Na[MCp(CO)3] (M = W or Mo, Cp = cyclopentadienyl) was explored. When R = H, the triangular clusters [PtM2Cp2(CO)5(μ-dppa)] (M = W, 4; M = Mo, 5), in which the diphosphane ligand bridges a Pt-M bond, were obtained as the only products. When R = −(CH2)9CH3, isomeric mixtures of the triangular clusters [PtM2Cp2(CO)5{Ph2PN(R)PPh2-P,P}], in which the diphosphane ligand chelates the Pt center (M = W, 11; M = Mo, 13) or bridges a Pt–M bond (M = W, 12; M = Mo, 14), were obtained. Irrespective of the M/Pt ratio used when R = −(CH2)9CH3, the reaction of [PtCl2{Ph2PN(R)PPh2-P,P}] with Na[MCp(CO)3] in acetonitrile stopped at the monosubstitution stage with the formation of [PtCl{MCp(CO)3}{Ph2PN(R)PPh2-P,P}] (R = −(CH2)9CH3, M = W, 9; M = Mo, 10), which are the precursors to the trinuclear clusters formed in THF when excess carbonylmetalate was used. The dynamic behavior of the dppa derivatives 4 and 5 in solution as well as that of their carbonylation products 6 and 7, respectively, is discussed. Density functional calculations were performed to study the thermodynamics of formation of 4 and 5 and 11–14, to evaluate the relative stabilities of the chelated and bridged forms and to trace a possible pathway for the formation of the trinuclear clusters.

We have recently described the synthesis of the complex [(PHCy2)Pt1(m-PCy2){k2P,O-m-P(O)Cy2}Pt2(PHCy2)] (Pt-Pt) (1), the first unsymmetrical phosphinito bridged Pt(I) species.[1] The phosphinito bridge differentiates the charge distributions on the two platinum atoms as confirmed by NMR spectroscopy (dPt(1) = -4798 ppm, dPt(2) = -5207 ppm) and DFT studies. Complex 1 shows a rich chemistry as it reacts with nucleophiles [PHCy2, PCy3, P(S)HCy2],[2] protic species HX [P(OH)Cy2, PhSH, HF, HCl, HBr, HI, HBF4],[3, 4] and small molecules such as H2.[5] Recently, we started investigations on the reactivity of complex 1 towards Au and Ag based electrophiles. In this communication, it will be shown that, differently from the isolobal H+ (which attacks the phosphinito oxygen and migrates onto the Pt-Pt bond),3 the [Ag(PPh3)]+ electrophile attacks complex 1 selectively to the Pt2-mP bond to afford the cationic cluster [(PHCy2)Pt1(m-PCy2){k2P,O-m-P(O)Cy2}Pt2{m- -Ag(PPh3)}(PHCy2)]+ (Pt–Pt) (2+) in which the [Ag(PPh3)]+ moiety bridges the mP-Pt2 bond. Analogous reactivity is observed also when phosphane free electrophiles such as AgOTf, AgBF4, AgClO4 and AgCl are used. Moreover, the reactivity of 1 towards Au(I) electrophiles such as AuCl and [Au(PPh3)Cl] was dependent on the reagent and on the experimental conditions. references: 1. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.; Suranna, G. P.; Ciccarella, G.; Englert, U.; Eur. J. Inorg. Chem., 2005, 4607–4616. 2. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.; Polini, F.; Re, N.; Englert, U.; Inorg. Chem., 2008, 47, 4785–4795. 3. Latronico, M.; Polini, F.; Gallo, V.; Mastrorilli, P; Calmuschi-Cula B.; Englert, U.; Re, N.; Repo T., Raisanen M.; Inorg. Chem., 2008, 47, 9979-9796. 4. M. Latronico, P. Mastrorilli, V. Gallo, M.M.Dell’Anna, F. Creati, N. Re, U. Englert, Inorg. Chem. 2011, 50, 3539–3558 5. Mastrorilli P., Latronico M., Gallo V., Polini F., Re N., Marrone A., Gobetto R., Ellena S.. J. Am. Chem. Soc. 2010, 132, 4752–4765

The reactivity of the phosphinito bridged Pt(I) complex [(PHCy2)Pt1(μ-PCy2){κ2P,O-μ- P(O)Cy2}Pt2(PHCy2)](Pt–Pt) (1) towards Au(I) and Ag(I) electrophiles was explored. Treatment of 1 with AuCl yielded the dichloro Pt(II) complex [(Cl)(PHCy2)Pt (μ-PCy2){κ210 P,O-μ-P(O)Cy2)Pt (Cl)(PHCy2)] (4), while [Au(PPh3)Cl] in thf (or toluene) caused ligand exchange resulting in the formation of [(PPh3)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt–Pt) (7) and [(PPh3)Pt(μ-PCy2){κ2P,O- μ-P(O)Cy2}Pt(PPh3)](Pt–Pt) (8). With [Au(PPh3)OTf] (independently from the solvent) or with [Au(PPh3)Cl] (only in dichloromethane), reaction with 1 gave [(PHCy2)Pt1(μ-PCy2){κ2P,O-μ- P(O)Cy2}Pt215 {μ-Au(PPh3)}(PHCy2)]X(Pt–Pt) ([6]X, X = OTf, Cl) clusters in which the [Au(PPh3)] moiety bridges the μP-Pt2 bond. The [Ag(PPh3)]+ electrophile attacks complex 1 selectively at the Pt2-μP bond to afford, at low T, the cationic cluster [(PHCy2)Pt1(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt2{μ- Ag(PPh3)}(PHCy2)]+(Pt–Pt) (10+) in which the [Ag(PPh3)]+ moiety bridges the μP-Pt2 bond. Clusters analogous to 10+, but without PPh3 bonded to Ag, are obtained from reactions of 1 with AgOTf, AgBF4, AgClO4 and AgCl.

Nutritional features of table grapes are the result of a complex combination of human practices with weather and environmental conditions. In the present study, the influence of agronomical practices on the chemical composition of commercial table grapes was studied by simple and fast Nuclear Magnetic Resonance (NMR)-based methods. In particular, variability of grape composition was evaluated considering primary metabolites, the compounds directly involved in growth and development of fruits and reliably detected by NMR spectroscopy. Three case studies of increasing complexity were examined. Primarily, it was found that inter-vineyard composition variability has a greater discriminating effect than intra-vineyard variability. The quantities of glucose, fructose, arginine and ethanol are the most dependent on farming practices. The comparison between organic and conventional productions (cv. Superior Seedless) showed a higher sugar content for the conventional practices, resulting in a higher sugar-to-acid ratio. For cultivars Red Globe and Italia, the factors most affected by farming practices were the glucose-to-fructose ratio and the amounts of arginine and ethanol.

The rational synthesis of dinuclear asymmetric phosphanido derivatives of palladium and platinum(II), [NBu4][(R-F)(2)M(mu-PPh2)(2)M'(kappa(2),N,C-C13H8N)] (R-F = C6F5; M = M' = Pt, 1; M = Pt, M' = Pd, 2; M = Pd, M' = Pt, 3; M = M' = Pd, 4), is described. Addition of I-2 to 1-4 gives complexes [(R-F)(2)M-II(mu-PPh2)(mu-I)Pd-II{PPh2(C13H8N)}] (M = M' = Pt, 6; M = Pt, M' = Pd, 7; M = M' = Pd, 8; M = Pd, M' = Pt 10) which contain the aminophosphane PPh2(C13H8N) ligand formed through a Ph2P/(CN)-N-boolean AND reductive coupling on the mixed valence M(II)-M'(IV) [NBu4][(R-F)(2)M-II(mu-PPh2)(2)M'(IV)(kappa(2),N,C- C13H8N)I-2] complexes, which were identified for M-II = Pd, M'(IV) = Pt (9), and isolated for M-II = Pt, M'(IV) = Pt (5). Complex 5 showed an unusual dynamic behavior consisting in the exchange of two phenyl groups bonded to different P atoms, as well as a "through space" spin-spin coupling between ortho-F atoms of the pentafluorophenyl rings.

The complex trans-[PtCl(PCy2)(PHCy2)2] (1) possesses a terminal phosphanido group (PCy2) and a chloride ligand, which render it a good candidate for the synthesis of phosphanido- bridged heterodimetallic species (PHCy2)2Pt(μ- PCy2)M–L by reaction either with carbonyl metalates, as metal-based nucleophiles, or with metal-based electrophiles. The heterodinuclear complexes [(PHCy2)2Pt(μ-PCy2)Co- (CO)3](Pt–Co) (2), [(PHCy2)2Pt(μ-PCy2)Mo(CO)2Cp](Pt–Mo) (3), and [(PHCy2)2Pt(μ-PCy2)W(CO)2Cp](Pt–W) (4) are obtained by reaction of 1 with the carbonyl metalates Na[Co- (CO)4], Na[Mo(CO)3Cp] and Na[W(CO)3Cp], respectively. Although 2 is reluctant to react with carbon monoxide, 3 and 4 are promptly carbonylated under ambient conditions to afford mixtures of the cis and trans isomers of [(PHCy2)(CO)- Pt(μ-PCy2)M(CO)2Cp] (M = Mo or W), which interconvert through dissociation/reassociation of the CO ligand coordinated to the Pt centre. The reaction of 1 with AuCl(PPh3) leads to the formation of the trinuclear Pt2Au complexes cisand trans-[{Cl(PHCy2)2Pt(μ-PCy2)}2Au]Cl (cis- and trans- [8]Cl), in which a Au atom bridges two molecules of 1 through the originally terminal phosphanide ligands.

The reactivity of the dinuclear platinum(III) derivative [(RF)2PtIII(μ-PPh2)2PtIII(RF)2](Pt−Pt) (RF = C6F5) (1) toward OH−, N3 −, and NCO− was studied. The coordination of these nucleophiles to a metal center evolves with reductive coupling or reductive elimination between a bridging diphenylphosphanido group and OH−, N3 −, and NCO− or C6F5 groups and formation of P−O, P−N, or P−C bonds. The addition of OH− to 1 evolves with a reductive coupling with the incoming ligand, formation of a P−O bond, and the synthesis of [NBu4]2[(RF)2PtII(μ-OPPh2)(μ-PPh2)- PtII(RF)2] (3). The addition of N3 − takes place through two ways: (a) formation of the P−N bond and reductive elimination of PPh2N3 yielding [NBu4]2[(RF)2PtII(μ-N3)(μ-PPh2)PtII(RF)2] (4a) and (b) formation of the P−C bond and reductive coupling with one of the C6F5 groups yielding [NBu4][(RF)2PtII(μ-N3)(μ- PPh2)PtII(RF)(PPh2RF)] (4b). Analogous behavior was shown in the addition of NCO− to 1 which afforded [NBu4]2[(RF)2PtII(μ-NCO)(μ-PPh2)PtII(RF)2] (5a) and [NBu4][(RF)2PtII(μ-NCO)(μ-PPh2)PtII(RF)(PPh2RF)] (5b). In the reaction of the trinuclear complex [(RF)2PtIII(μ-PPh2)2PtIII(μ-PPh2)2PtII(RF)2](PtIII−PtIII) (2) with OH− or N3 −, the coordination of the nucleophile takes place selectively at the central platinum(III) center, and the PPh2/OH− or PPh2/N3 − reductive coupling yields the trinuclear [NBu4]2[(RF)2PtII(μ-Ph2PO)(μ-PPh2)PtII(μ-PPh2)2PtII(RF)2] (6) and [NBu4]- [(RF)2Pt1(μ3-Ph2PNPPh2)(μ-PPh2)Pt2(μ-PPh2)Pt3(RF)2](Pt2−Pt3) (7). Complex 7 is fluxional in solution, and an equilibrium consisting of Pt−Pt bond migration was ascertained by 31P EXSY experiments.

In this study, non-targeted (1)H NMR fingerprinting was used in combination with multivariate statistical techniques for the classification of Italian sweet cherries based on their different geographical origins (Emilia Romagna and Puglia). As classification techniques, Soft Independent Modelling of Class Analogy (SIMCA), Partial Least Squares Discriminant Analysis (PLS-DA), and Linear Discriminant Analysis (LDA) were carried out and the results were compared. For LDA, before performing a refined selection of the number/combination of variables, two different strategies for a preliminary reduction of the variable number were tested. The best average recognition and CV prediction abilities (both 100.0%) were obtained for all the LDA models, although PLS-DA also showed remarkable performances (94.6%). All the statistical models were validated by observing the prediction abilities with respect to an external set of cherry samples. The best result (94.9%) was obtained with LDA by performing a best subset selection procedure on a set of 30 principal components previously selected by a stepwise decorrelation. The metabolites that mostly contributed to the classification performances of such LDA model, were found to be malate, glucose, fructose, glutamine and succinate.

The dynamic behavior in solution of eight mono-hapto tetraphosphorus transition metal-complexes, trans-[Ru(dppm)2(H)(η1-P4)]BF4 ([1]BF4), trans-[Ru(dppe)2(H)(η1-P4)]BF4 ([2]BF4), [CpRu(PPh3)2(η1-P4)]PF6 ([3]PF6), [CpOs(PPh3)2(η1-P4)]PF6 ([4]PF6), [Cp*Ru(PPh3)2(η1-P4)]PF6 ([5]PF6), [Cp*Ru(dppe)(η1-P4)]PF6 ([6]PF6), [Cp*Fe(dppe)(η1-P4)]PF6 ([7]PF6), [(triphos)Re(CO)2(η1-P4)]OTf ([8]OTf), and of three bimetallic Ru(μ,η1:2-P4)Pt species [{Ru(dppm)2(H)}(μ,η1:2-P4){Pt(PPh3)2}]BF4 ([1-Pt]BF4), [{Ru(dppe)2(H)}(μ,η1:2-P4){Pt(PPh3)2}]BF4 ([2-Pt]BF4), [{CpRu(PPh3)2)}(μ,η1:2-P4){Pt(PPh3)2}]BF4 ([3-Pt]BF4), [dppm=bis(diphenylphosphanyl)methane; dppe=1,2-bis(diphenylphosphanyl)ethane; triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane; Cp=η5-C5H5; Cp*=η5-C5Me5] was studied by variable-temperature (VT) NMR and 31P{1H} exchange spectroscopy (EXSY). For most of the mononuclear species, NMR spectroscopy allowed to ascertain that the metal-coordinated P4 molecule experiences a dynamic process consisting, apart from the free rotation about the MP4 axis, in a tumbling movement of the P4 cage while remaining chemically coordinated to the central metal. EXSY and VT 31P NMR experiments showed that also the binuclear complex cations [1-Pt]+–[3-Pt]+ are subjected to molecular motions featured by the shift of each metal from one P to an adjacent one of the P4 moiety. The relative mobility of the metal fragments (Ru vs. Pt) was found to depend on the co-ligands of the binuclear complexes. For complexes [2]BF4 and [3]PF6, MAS, 31P NMR experiments revealed that the dynamic processes observed in solution (i.e., rotation and tumbling) may take place also in the solid state. The activation parameters for the dynamic processes of complexes 1+, 2+, 3+, 4+, 6+, 8+ in solution, as well as the X-ray structures of 2+, 3+, 5+, 6+ are also reported. The data collected suggest that metal-coordinated P4 should not be considered as a static ligand in solution and in the solid state.

Among the various vineyard treatments adopted in recent years for table-grape cultivation, there has been a significant use of plant growth regulators (PGRs) and girdling to increase berry size and yield. In particular, an increase in the application of forchlorfenuron (CPPU) and gibberellic acid (GA3) for many seeded and seedless table-grape cultivars has been registered in several countries. In this two-year study, girdling at berry set, gibberellic acid (10 mg/L) applied at berry diameter of 10 to 11 mm, and forchlorfenuron (9.75 mg/L) applied at berry diameter of 11 to 12 mm were investigated to verify their effects on berry size, yield, and chemical and metabolic characteristics of Italia grapes. In general, at harvest all treatments significantly increased berry diameter, length, and weight and consequent cluster weight and yield/vine compared to an untreated control. The treatments showed significant differences for the colorimetric parameters, in particular a higher value of hue for berries treated with GA3 and CPPU, thus shifting the skin color from yellow toward yellow-green. Metabolomic study carried out by nuclear magnetic resonance spectroscopy combined with principal component analysis indicated that metabolic profile depends on the year and, in each year, the effect of treatments consisted of a slight variation of amino acid content. Treatments effects were more pronounced in the year characterized by a cooler summer.

The reaction of the neutral binuclear complexes [(R(F))(2)Pt(mu-PPh(2))(2)M(Phen)1 (phen = 1,10-phenanthroline, R(F) = C(6)F(5); M = Pt, 1; M = Pd, 2) with AgClO(4) or [Ag(OClO(3))(PPh(3))] affords the trinuclear complexes [AgPt(2)(mu-PPh(2))(2)(R(F))(2)(Phen)(OClO(3))] (7a) or [AgPtM(mu-PPh(2))(2)(RF)(2)(Phen)(PPh(3))] [ClO(4)] (M = Pt, 8; M = Pd, 9), which display an "open-book" type structure and two (7a) or one (8,9) Pt Ag bonds. The neutral diphosphine complexes [(R(F))(2)Pr(mu-PPh(2))(2)m(P P)] (P P = 1,2-bis(diphenylphosphino)methane, dppm, M = Pt, 3; M = Pd, 4; P P = 1,2-bis(diphenylphosphino)ethane, dppe, M = Pt, 5; M = Pd, 6) react with AgClO(4) or [Ag(OClO(3))(PPh(3))], and the nature of the resulting complexes is dependent on both M and the diphosphine. The dppm Pt Pt complex 3 reacts with [Ag(OClO(3))(PPh(3))], affording a silver adduct 10 in which the Ag atom interacts with the Pt atoms, while the dppm Pt Pd complex 4 reacts with [Ag(OClO(3))(PPh(3))], forming a 1:1 mixture of [AgPdPt(mu-PPh(2))(2)(RF)(2)(OClO(3))(dppm)] (11), in which the silver atom is connected to the Pt-Pd moiety through Pd (mu-PPh(2)) Ag and Ag-P(k'-dppm) interactions, and [AgPdPt(mu-PPh(2))(2) (R(F))(2)(OClO(3))(PPh(3))(2)] [ClO(4)] (12). The reaction of complex 4 with AgClO(4) gives the trinuclear derivative 11 as the only product. Complex 11 shows a dynamic process in solution in which the silver atom interacts alternatively with both Pd-mu PPh(2) bonds. When P-P is dppe, both complexes 5 and 6 react with AgClO(4) or [Ag(OClO(3))(PPh(3))], forming the saturated complexes (M = Pt, 13; Pd, 14), which are the result of an oxidation followed by a PPh(2)/C(6)F(5) reductive coupling. Finally, the oxidation of trinuclear derivatives [(R(F))(2)Pt(II)(mu-PPh(2))(2)Pt(II)(mu-4PPh(2))(2)Pt(II)L(2)] (L(2) = phen, 15; L = PPh(3), 16) by AgClO(4) results in the formation of the unsaturated 46 VEC complexes [(R(F))(2)Pt(III)(mu-PPh(2))(2)Pt(III)(mu-PPh(2))(2)Pt(II)L(2)][ClO(4)](2) (17 and 18, respectively) which display Pt(III)-Pt(III) bonds.

Neutral, end-on bound white-phosphorus complexes with unprecedented stability in the solid state and solution were synthesized (see structure: gray C, blue Mn, red O, violet P). While the C5(4-nBuC6H4)5 ligands are stationary at low temperature on the NMR timescale, the P4 ligands rotate rapidly. Despite the unfavorable γP/γH ratio, a heteronuclear Overhauser effect between the protons in ortho position and the basal P atoms was detected.

The reactions of [Ag(OClO3)(PPh3)] with [NBu4][(C6F5)2Pt(μ- PPh2)2M(hq)], [NBu4][(C6F5)2Pt(μ-PPh2)2M(bq)], [NBu4]- [(C6F5)2Pt(μ-PPh2)2M(pic)] and [NBu4][(C6F5)2Pt(μ-PPh2)2Pt- (C6F5)(tht)] (M = Pt, Pd; hq = 8-hydroxyquinolinate, bq = benzoquinolinate, pic = picolinate, tht = tetrahydrothiophene) afford the corresponding neutral adducts [(C6F5)2Pt- (μ-PPh2)2(μ-AgPPh3)M(bq)] (M = Pt, 1; Pd, 2), [(C6F5)2Pt(μ- PPh2)2(μ-AgPPh3)M(hq)] (M = Pt, 3; Pd, 4) [(C6F5)2Pt(μ-PPh2)2- (μ-AgPPh3)Pt(C6F5)(tht)] (5) and [(C6F5)2Pt(μ-PPh2)2M(pic- AgPPh3)] (M = Pt, 6; Pd, 7) as yellow solids. The XRD structures of 1–5, in which a [AgPPh3]+ moiety bridges the metal centres, were confirmed in solution at low temperature. At room temperature, a dynamic process for the [AgPPh3]+ moiety, which passes from the top to the bottom part of the molecules 1–5, was ascertained. For 6 and 7, the XRD analyses revealed structures in which the [AgPPh3]+ moiety is linked to the picolinate oxygen atom bonded to the M centre; however, although such a structure was confirmed in solution for the Pt–Pd species 7, the stable form of the Pt–Pt species 6 in solution is that with the [AgPPh3]+ moiety bridging the metal centres.

The dinuclear anionic complexes [NBu4][(R-F)(2)M-II(mu-PPh2)(2)M'(II)((NO)-O-boolean AND)](R-F = C6F5. (NO)-O-boolean AND = 8-hydroxyquinolinate, hq; M = M' = Pt 1; Pd 2; M = Pt, M' = Pd, 3. (NO)-O-boolean AND = o-picolinate, pic; M = Pt, M' = Pt, 4; Pd, 5) are synthesized from the tetranuclear [NBu4](2)[{(R-F)(2)Pt(mu-PPh2)(2)M(mu-Cl)}(2)] by the elimination of the bridging Cl as AgCl in acetone, and coordination of the corresponding N,O-donor ligand (1, 4, and 5) or connecting the fragments "cis-[(R-F)(2)M(mu-PPh2)(2)](2-)" and "M'((NO)-O-boolean AND)" (2 and 3). The electrochemical oxidation of the anionic complexes 1-5 occurring under HRMS(+) conditions gave the cations [(R-F)(2)M(mu-PPh2)(2)M'((NO)-O-boolean AND)](+), presumably endowed with a M(III),M'(III) core. The oxidative addition of I-2 to the 8-hydroxyquinolinate complexes 1-3 triggers a reductive coupling between a PPh2 bridging ligand and the N,O-donor chelate ligand with formation of a P-O bond and ends up in complexes of platinum(II) or palladium(II) of formula [(R-F)(2)M-II(mu-I)(mu-PPh2)M'(II)(P,N-PPh(2)hq)], M = M' = Pt 7, Pd 8; M = Pt, M' = Pd, 9. Complexes 7-9 show a new Ph2P-OC9H6N (Ph2P-hq) ligand bonded to the metal center in a P,N-chelate mode. Analogously, the addition of I-2 to solutions of the o-picolinate complexes 4 and 5 causes the reductive coupling between a PPh2 bridging ligand and the starting N,O-donor chelate ligand with formation of a P-O bond, forming Ph2P-OC6H4NO (Ph2P-pic). In these cases, the isolated derivatives [NBu4][(Ph2P-pic)(R-F)Pt-II(mu-I)(mu-PPh2)M-II(R-F)I] (M = Pt 10, Pd 11) are anionic, as a consequence of the coordination of the resulting new phosphane ligand (Ph2P-pic) as monodentate P-donor, and a terminal iodo group to the M atom. The oxidative addition of I-2 to [NBu4][(R-F)(2)Pt-II(mu-PPh2)(2)Pt-II(acac)] (6) (acac = acetylacetonate) also results in a reductive coupling between the diphenylphosphanido and the acetylacetonate ligand with formation of a P-O bond and synthesis of the complex [NBu4][(R-F)(2)Pt-II(mu-I)(mu-PPh2)Pt-II(Ph2P-acac)I] (12). The transformations of the starting complexes into the products containing the P-O holds passes through mixed valence M(II),M'(IV) intermediates which were detected, for M = M' = Pt, by spectroscopic and spectrometric measurements.

Si occupa della valorizzazione dei prodotti agroalimentari mediante lo sviluppo di innovativi sistemi analitici. Combina analisi di Risonanza Magnetica Nucleare (NMR), analisi statistica multivariata e implementazione di sistemi esperti di classificazione al fine di realizzare il controllo e l’ottimizzazione dei processi produttivi. Sperimenta nuovi metodi di prova in conformità ai requisiti normativi internazionali utilizzando strumentazione all’avanguardia. Ha sviluppato protocolli di analisi di varie matrici alimentari (uva da tavola, uva da vino, vino, ciliegie, melograno, grano e farine) con la NMR e si propone di valorizzare le conoscenze scientifiche derivanti dagli studi condotti in materia di chimica degli alimenti presso il DICATECh del Politecnico di Bari.