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.

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 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.

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.