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118 results on '"Femoni, Cristina"'

4. Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4– Displaying a Defective Structure

Author

Cesari, Cristiana, primary, Berti, Beatrice, additional, Funaioli, Tiziana, additional, Femoni, Cristina, additional, Iapalucci, Maria Carmela, additional, Pontiroli, Daniele, additional, Magnani, Giacomo, additional, Riccò, Mauro, additional, Bortoluzzi, Marco, additional, Vivaldi, Federico Maria, additional, and Zacchini, Stefano, additional

Published
2022
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9. Synthesis and electrochemistry of new Rh-centered and conjuncto rhodium carbonyl clusters: x-ray structure of [[[NEt.sub.4]].sub.3][[Rh.sub.15][(CO).sub.27]], [[NEt.sub.4].sub.3][[Rh.sub.15][(CO).sub.25][(MeCN).sub.2]].2MeCN, and [[NEt.sub.4].sub.3][[Rh.sub.17][(CO).sub.37]

Author

Collini, Davide, De Biani, Fabrizia Fabrizi, Fedi, Serena, Femoni, Cristina, Kaswalder, Francesco, Iapalucci, Maria Carmela, Longoni, Giuliano, Tiozzo, Cristina, Zacchini, Stefano, and Zanello, Piero

Subjects
Rhodium -- Structure, Rhodium -- Chemical properties, Carbonyl compounds -- Chemical properties, Carbonyl compounds -- Structure, Electrochemical analysis, Chemistry
Abstract

The study describes the synthesis and electrochemistry of the new Rh-centered and conjuncto rhodium carbonyl clusters. The x-ray structure of [[[NEt.sub.4]].sub.3][[Rh.sub.15][(CO).sub.27]], [[NEt.sub.4].sub.3][[Rh.sub.15][(CO).sub.25][(MeCN).sub.2]].2MeCN, and [[NEt.sub.4].sub.3][[Rh.sub.17][(CO).sub.37] is also explained.

Published
2007

13. Redox behavior of (H(sub 6-n)Ni(sub 38)Pt(sub 6)(CO)(sub 48))(super n-) (n = 4-6) anions: a series of metal carbonyl clusters displaying electron-sink features

Author

Biani, Fabrizia Fabrizi de, Femoni, Cristina, Iapalucci, Maria Carmela, Longoni, Giuliano, Zanello, Piero, and Ceriotti, Alessandro

Subjects
Oxidation-reduction reaction -- Research, Carbonyl compounds -- Research, Coordination compounds -- Research, Chemistry
Abstract

Research was conducted to examine the chemical and electrochemical redox behavior of the bimetallic (H(sub 6-n)Ni(sub 38)Pt(sub 6)(CO)(sub 48))(super n-) (n = 4-6) anions to demonstrate that they exhibit electron-sink features encompassing up to six different oxidation states. As a corollary, the experiments also provide an indirect proof of the presence of hydride atoms where n = 4 and 5.

Published
1999

20. Polypyridyl ruthenium(II) complexes with tetrazolate-based chelating ligands: synthesis, reactivity and electrochemical and photophysical pfroperties

Author

Stagni, Stefano, Orselli, Enrico, Palazzi, Antonio, Cola, Luisa De, Zacchini, Stefano, Femoni, Cristina, Marcaccio, Massimo, Paolucci, Francesco, and Zanarini, Simone

Subjects
Coordination compounds -- Chemical properties, Nuclear magnetic resonance spectroscopy -- Technology application, Pyridazine -- Chemical properties, Pyridazine -- Electric properties, Ruthenium -- Chemical properties, Technology application, Chemistry
Abstract

The studies of pyridyl-tetrazolate or pyrazinyl-tetrazolates as anionic bpy-type ligands for Ru(II) polypyridyl complexes where (pby = 2,2'-bipyridyl) is reported.

Published
2007

22. Interstitial Bismuth Atoms in Icosahedral Rhodium Cages: Syntheses, Characterizations, and Molecular Structures of the [Bi@Rh12(CO)27]3–, [(Bi@Rh12(CO)26)2Bi]5–, [Bi@Rh14(CO)27Bi2]3–, and [Bi@Rh17(CO)33Bi2]4– Carbonyl Clusters

Author

Femoni, Cristina, primary, Bussoli, Guido, additional, Ciabatti, Iacopo, additional, Ermini, Marco, additional, Hayatifar, Mohammad, additional, Iapalucci, Maria C., additional, Ruggieri, Silvia, additional, and Zacchini, Stefano, additional

Published
2017
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25. N,N'-dialkylimidazolium chloroplatinate (II), chloroplatinate (IV) and chloroiridate (IV) salts and an N-heterocyclic carbene complex of platinum(II): synthesis in ionic liquids and crystal structures

Author

Hasan, Masihul, Kozhevnikov, Ivan V., Siddiqui, Rafiq M H, Femoni, Cristina, Steiner, Alexander, and Winterton, Neil

Subjects
Carbides -- Optical properties, Platinum -- Optical properties, Chemical synthesis -- Research, Chemistry
Abstract

The synthesis, thermostability and single crystal x-ray structure of 1-ethyl-3-methylimidazolium and 1-Eta-butyl-3-methylimidazolium is studied using a research. An exploration of a platinum group metal in ionic liquid is done.

Published
2001

30. Polymerization Isomerism in [{MFe(CO)4}n]n−(M = Cu, Ag, Au; n= 3, 4) Molecular Clusters Supported by Metallophilic Interactions

Author

Berti, Beatrice, Bortoluzzi, Marco, Cesari, Cristiana, Femoni, Cristina, Iapalucci, Maria Carmela, Mazzoni, Rita, Vacca, Federico, and Zacchini, Stefano

Abstract

Triangular clusters [{MFe(CO)4}3]3–(M = Cu, 4; Ag, 5; Au, 6) were selectively obtained by heating Fe(CO)4(MIMes)2(M = Cu, 1; Ag, 2; Au, 3; IMes = C3N2H2(C6H2Me3)2). 1–3were synthesized by reacting Na2[Fe(CO)4]·2thf with 2 equiv of M(IMes)Cl. As previously described, the direct reactions of Na2[Fe(CO)4]·2thf with one equivalent of M(I) salts resulted in the triangular cluster [{CuFe(CO)4}3]3–for Cu, whereas the square clusters [{MFe(CO)4}4]4–were formed for Ag and Au. Thus, depending on the synthetic protocol adopted, both the triangular [{MFe(CO)4}3]3–and square [{MFe(CO)4}4]4–polymerization isomers can be selectively obtained, at least for Ag and Au. Polymerization isomerism, that is two compounds having the same elemental compositions but different molecular weights, was investigated in [{MFe(CO)4}n]n−(n= 3, 4; M = Cu, Ag, Au) by means of structural and theoretical methods and the role of metallophilic interactions was computationally studied by means of the atoms-in-molecules (AIM) approach.

Published
2019
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35. Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni11P(CO)18]3–and [H6–nNi31P4(CO)39]n−(n= 4 and 5)

Author

Capacci, Chiara, Ciabatti, Iacopo, Femoni, Cristina, Iapalucci, Maria Carmela, Funaioli, Tiziana, Zacchini, Stefano, and Zanotti, Valerio

Abstract

The reaction of [NEt4]2[Ni6(CO)12] in thf with 0.5 equiv of PCl3affords the monophosphide [Ni11P(CO)18]3–that in turn further reacts with PCl3resulting in the tetra-phosphide carbonyl cluster [HNi31P4(CO)39]5–. Alternatively, the latter can be obtained from the reaction of [NEt4]2[Ni6(CO)12] in thf with 0.8–0.9 equiv of PCl3. The [HNi31P4(CO)39]5–penta-anion is reversibly protonated by strong acids leading to the [H2Ni31P4(CO)39]4–tetra-anion, whereas deprotonation affords the [Ni31P4(CO)39]6–hexa-anion. The latter is reduced with Na/naphthalene yielding the [Ni31P4(CO)39]7–hepta-anion. In order to shed light on the polyhydride nature and redox behavior of these clusters, electrochemical and spectroelectrochemical studies were carried out on [Ni11P(CO)18]3–, [HNi31P4(CO)39]5–, and [H2Ni31P4(CO)39]4–. The reversible formation of the stable [Ni11P(CO)18]4–tetra-anion is demonstrated through the spectroelectrochemical investigation of [Ni11P(CO)18]3–. The redox changes of [HNi31P4(CO)39]5–show features of chemical reversibility and the vibrational spectra in the νCOregion of the nine redox states of the cluster [HNi31P4(CO)39]n–(n= 3–11) are reported. The spectroelectrochemical investigation of [H2Ni31P4(CO)39]4–revealed the presence of three chemically reversible reduction processes, and the IR spectra of [H2Ni31P4(CO)39]n–(n= 4–7) have been recorded. The different spectroelectrochemical behavior of [HNi31P4(CO)39]5–and [H2Ni31P4(CO)39]4–support their formulations as polyhydrides. Unfortunately, all the attempts to directly confirm their poly hydrido nature by 1H NMR spectroscopy failed, as previously found for related large metal carbonyl clusters. Thus, the presence and number of hydride ligands have been based on the observed protonation/deprotonation reactions and the spectroelectrochemical experiments. The molecular structures of the new clusters have been determined by single-crystal X-ray analysis. These represent the first examples of structurally characterized molecular nickel carbonyl nanoclusters containing interstitial phosphide atoms.

Published
2018
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41. Heteroleptic Chini-Type Platinum Clusters: Synthesis and Characterization of Bis-Phospine Derivatives of [Pt3n(CO)6n]2–(n= 2–4)

Author

Cesari, Cristiana, Ciabatti, Iacopo, Femoni, Cristina, Iapalucci, Maria Carmela, Mancini, Federica, and Zacchini, Stefano

Abstract

The reactions of [Pt3n(CO)6n]2–(n= 2–4) homoleptic Chini-type clusters with stoichiometric amounts of Ph2PCH2CH2PPh2(dppe) result in the heteroleptic Chini-type clusters [Pt6(CO)10(dppe)]2–, [Pt9(CO)16(dppe)]2–, and [Pt12(CO)20(dppe)2]2–. Their formation is accompanied by slight amounts of neutral species such as Pt4(CO)4(dppe)2, Pt6(CO)6(dppe)3, and Pt(dppe)2. A similar behavior was observed with the chiral ligand R-Ph2PCH(Me)CH2PPh2(R-dppp), and two isomers of [Pt9(CO)16(R-dppp)]2–were identified. All the new species were spectroscopically characterized by means of IR and 31P NMR, and their structures were determined by single-crystal X-ray diffraction. The results obtained are compared to those previously reported for monodentate phosphines, that is, PPh3, as well as more rigid bidentate ligands, that is, CH2C(PPh2)2(P^P), CH2(PPh2)2(dppm), and o-C6H4(PPh2)2(dppb). From a structural point of view, functionalization of anionic platinum Chini clusters preserves their triangular Pt3units, whereas the overall trigonal prismatic structures present in the homoleptic clusters are readily deformed and transformed upon functionalization. Such transformations may be just local deformations, as found in [Pt9(CO)16(dppe)]2–, [Pt9(CO)16(R-dppp)]2–, [Pt12(CO)22(PPh3)2]2–, and [Pt9(CO)16(PPh3)2]2–; an inversion of the cage from trigonal prismatic to octahedral, as observed in [Pt6(CO)10(dppe)]2–and [Pt6(CO)10(PPh3)2]2–; the reciprocal rotation of two trigonal prismatic units with the loss of a Pt–Pt contact as found in [Pt12(CO)20(dppe)2]2–.

Published
2017
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42. Synthesis, Structure, and Spectroscopic Characterization of [H8−nRh22(CO)35]n−(n= 4, 5) and [H2Rh13(CO)24{Cu(MeCN)}2]−Clusters: Assessment of CV and DPV As Techniques to Circumstantiate the Presence of Elusive Hydride Atoms

Author

Collini, Davide, primary, Fabrizi De Biani, Fabrizia, additional, Dolzhnikov, Dmitriy S., additional, Femoni, Cristina, additional, Iapalucci, Maria C., additional, Longoni, Giuliano, additional, Tiozzo, Cristina, additional, Zacchini, Stefano, additional, and Zanello, Piero, additional

Published
2011
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44. Syntheses, Structures, and Electrochemistry of the Defective ccp[Pt33(CO)38]2–and the bcc[Pt40(CO)40]6–Molecular Nanoclusters

Author

Cattabriga, Enrico, Ciabatti, Iacopo, Femoni, Cristina, Funaioli, Tiziana, Iapalucci, Maria Carmela, and Zacchini, Stefano

Abstract

The molecular [Pt33(CO)38]2–nanocluster was obtained from the thermal decomposition of Na2[Pt15(CO)30] in methanol. The reaction of [Pt19(CO)22]4–with acids (1–2 equiv) affords the unstable [Pt19(CO)22]3–trianion, which evolves with time leading eventually to the [Pt40(CO)40]6–hexa-anion. The total structures of both nanoclusters were determined via single-crystal X-ray diffraction. [Pt33(CO)38]2–displays a defective ccpPt33core and shows that localized deformations occur in correspondence of atomic defects to “repair” them. In contrast, [Pt40(CO)40]6–shows a bccPt40core and represents the largest Pt cluster with a body-centered structure. The rich electrochemistry of the two high-nuclearity platinum carbonyl clusters was studied by cyclic voltammetry and electrochemical in situ Fourier transform infrared spectroscopy. The redox changes of [Pt33(CO)38]2–show features of chemical reversibility and electrochemical quasi-reversibility, and the vibrational spectra in the CO stretching region of the nine redox forms of the cluster [Pt33(CO)38]n(n= 0 to −4, −6 to −9) are reported. Almost all the redox processes exhibited by [Pt40(CO)40]6–are chemically and electrochemically reversible, and the eight oxidation states of [Pt40(CO)40] from −4 to −11 were spectroscopically characterized. The effect of the more regular bccPt-carbonyl cluster structure of [Pt40(CO)40]6–with respect to that of the defective ccpPt33core on the redox behavior is discussed.

Published
2016
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45. Octahedral Co-Carbide Carbonyl Clusters Decorated by [AuPPh3]+ Fragments: Synthesis, Structural Isomerism, and Aurophilic Interactions of Co6C(CO)12(AuPPh3)4.

Author

Ciabatti, Iacopo, Femoni, Cristina, Hayatifar, Mohammad, Iapalucci, Maria Carmela, Ienco, Andrea, Longoni, Giuliano, Manca, Gabriele, and Zacchini, Stefano

Subjects
*OCTAHEDRAL molecules, *STRUCTURAL isomerism, *X-ray crystallography, *DENSITY functional theory, *SOLID state chemistry, *SOLVENTS
Abstract

The Co6C(CO)12(AuPPh3)4 carbide carbonyl cluster was obtained from the reaction of [Co6C(CO)15]2- with Au(PPh3)Cl. This new species was investigated by variable-temperature 31P NMR spectroscopy, X-ray crystallography, and density functional theory methods. Three different solvates were characterized in the solid state, namely, Co6C(CO)12(AuPPh3)4 (I), Co6C(CO)12(AuPPh3)4·THF (II), and Co6C(CO)12(AuPPh3)4·4THF (III), where THF = tetrahydrofuran. These are not merely different solvates of the same neutral cluster, but they contain three different isomers of Co6C(CO)12(AuPPh3)4. The three isomers I-III possess the same octahedral [Co6C(CO)12]4- carbido-carbonyl core differently decorated by four [AuPPh3]+ fragments and showing a different Au(I)···Au(I) connectivity. Theoretical investigations suggest that the formation in the solid state of the three isomers during crystallization is governed by packing and van der Waals forces, as well as aurophilic and weak π-π and π-H interactions. In addition, the closely related cluster Co6C(CO)12(PPh3)(AuPPh3)2 was obtained from the reaction of [Co8C(CO)18]2- with Au(PPh3)Cl, and two of its solvates were crystallographically characterized, namely, Co6C(CO)12(PPh3)(AuPPh3)2·toluene (IV) and Co6C(CO)12(PPh3)(AuPPh3)2·0.5toluene (V). A significant, even if minor, effect of the cocrystallized solvent molecules on the structure of the cluster was observed also in this case. [ABSTRACT FROM AUTHOR]

Published
2014
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47. The Redox Chemistry of [Co6C(CO)15]2-: A Synthetic Route to New Co-Carbide Carbonyl Clusters.

Author

Ciabatti, Iacopo, Femoni, Cristina, Hayatifar, Mohammad, Iapalucci, Maria Carmela, Longoni, Giuliano, Pinzino, Calogero, Solmi, Matilde Valeria, and Zacchini, Stefano

Subjects
*COBALT compounds synthesis, *OXIDATION-reduction reaction, *ORGANOMETALLIC chemistry, *TETRAHYDROFURAN, *METAL clusters, *ELECTRON paramagnetic resonance spectroscopy
Abstract

The oxidation and reduction reactions of [Co6C- (CO)l5]2- have been studied in detail, leading to the isolation of several new Co-carbide carbonyl clusters. Thus, [Co6C(CO)15]2- reacts in tetrahydrofuran (THF) with oxidants such as HBF4-Et2O and [Cp2Fe][PF6], resulting first in the formation of the previously reported [Co6C(CO)14]-; then, in CH2Cl2, the new dicarbide [Co11C2(CO)23]2- is formed. The latter may be further oxidized, yielding the isostructural monoanion [Co11C2(CO)23]-, whereas its reduction with (cyclopentadienyl)2Co affords the unstable trianion [Co11C2(CO)23]3- which decomposes during workup. Oxidation of [Co6C(CO)15]2- in CH3CN with [C7H7][BF4] affords the same major products, and besides, the new monoacerylide [Co10(C2)- (CO)21]2- was obtained as side-product. Conversely, the reduction of [Co6C(CO)15]2- in THF with increasing amounts of Na/naphthalene results in the following species: [Co6C(CO),3]2-, [Cou(C2)(CO)22]³-, [Co7C(CO)15,]³-, [Co8C(CO)17]4-, [Co6C(CO)12]3-, and [Co(CO)4]-. The new [Co11CO)23]-, [Co11C2(CO)23]2-, [Col0(C2)(CO)21]2-, [Co8C(CO)17]4-, [Co6C(CO)12]3-, and [Co7C(CO)15]³ clusters were structurally characterized. Moreover, the paramagnetic species [Co11C2(CO)23]2- and [Co6C(CO)12]3- were investigated by means of electron paramagnetic resonance spectroscopy. Finally, electrochemical studies were performed on [Co11C2(CO)23]n- (n = 1-- 3). [ABSTRACT FROM AUTHOR]

Published
2014
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49. Intramolecular d10-d10 Interactions in a Ni6C(CO)9(AuPPh3)4 Bimetallic Nickel-Gold Carbide Carbonyl Cluster.

Author

Ciabatti, Iacopo, Femoni, Cristina, Iapalucci, Maria Carmela, lenco, Andrea, Longoni, Giuliano, Manca, Gabriele, and Zacchini, Stefano

Subjects
*NICKEL compounds, *CARBONYL compounds, *METAL clusters, *CHEMICAL reactions, *SOLID state chemistry, *DENSITY functionals, *SOLVENTS
Abstract

The Ni6C(CO)9(AuPPh3)4 bimetallic carbide carbonyl cluster was obtained from the reaction of [Ni9C(CO)17]2- with Au(PPh3)Cl. It contains a rare carbon-centered (distorted) Ni6C octahedral core decorated by four Au(PPh3) fragments. These are μ3-bonded to four contiguous Ni3-triangular faces and display weak intramolecular Au···Au d10-d10 interactions. The cluster has been characterized in the solid state on two different solvato crystals, i.e., Ni6C(CO)9(AuPPh3)4·THF and Ni6C(CO)9(AuPPh3)4·THF·0.5C6H14. The two solvates show some interesting differences concerning the weak Au···Au contacts. Density functional theory calculations have demonstrated that the presence of the two isomers is related to solid-state packing effects and not to the existence of two double minima in the potential energy surface. This, in turn, confirms that Au···Au d10-d10 interactions are rather soft and thus influenced also by weak van der Waals forces because of the interaction of the cluster with the cocrystallized solvent molecules. [ABSTRACT FROM AUTHOR]

Published
2013
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50. Synthesis, Structure, and Electrochemistry of the Ni-Au Carbonyl Cluster [Ni12Au(CO)24]3- and Its Relation to [Ni32Au6(CO)44]6-.

Author

Ciabatti, Iacopo, Femoni, Cristina, Iapalucci, Maria Carmela, Longoni, Giuliano, Zacchini, Stefano, Fedi, Serena, and de Biani, Fabrizia Fabrizi

Subjects
*CRYSTAL structure, *ELECTROCHEMISTRY, *METAL clusters, *CARBONYL compounds, *INORGANIC synthesis, *CHEMICAL reactions, *X-ray diffraction
Abstract

A detailed study of the reaction between [Ni6(CO)12]2- and [AuCl4]⁻ afforded the isolation of the new Ni--Au cluster [Ni12Au(CO)24]3- as well as identifying an improved synthesis for the previously reported [Ni32Au6(CO)44]6-. The new [Ni12Au(CO)24]3- cluster is composed by two [Ni6(CO)12]2- moieties coordinated to a central Au(I) ion, as determined by X-ray diffraction. It is noteworthy that the two [Ni6(CO)12]2- fragments display different geometries, i.e., trigonal antiprismatic (distorted octahedral) and distorted trigonal prismatic (monocapped square pyramidal). The chemical reactivity of these clusters and their electrochemical behavior have been studied. [Ni12Au(CO)24]3- is irreversibly transformed, upon electrochemical reduction, into Au(0) and [Ni6(CO)12]2-, followed by the reversible reduction of the latter homometallic cluster. Conversely, [Ni32Au6(CO)44]6- displays five reductions, with apparent features of reversibility, confirming the ability of larger metal carbonyl clusters to reversibly accept and release electrons. [ABSTRACT FROM AUTHOR]

Published
2012
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