New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN←PtCl2 backbonding vs. the IR νCN blue-shift dichotomy in organonitriles–platinum(ii) complexes. A thorough density functional theory – energy decomposition analysis study

For a series of organonitrile [RCN (R = Me, CF3, Ph, CH3Ph, CF3Ph)] ligands, the nature of the N–Pt bond in the related cis-/trans-(RCN)2PtCl2 complexes has been computationally investigated by Density Functional Theory. A fragment based bond analysis has been performed in the canonical Kohn–Sham molecular orbitals framework, and it has been ultimately assessed that this bond is characterized both by N→Pt σ and by N←Pt π contributions. Voronoi Deformation Density charges further confirms the occurrence of N←Pt π interactions. Moreover, the Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) method shows that the strength of the N←Pt π interaction is not negligible …

Spin state, electronic structure and bonding on C-scorpionate [Fe(II)Cl2(tpm)] catalyst: An experimental and computational study

Abstract The Fe(II) spin state in the condensed phase of [Fe(II)Cl2(tpm)] (tpm = [tris(pyrazol-1-yl)methane]; 1) catalyst has been determined through a combined experimental and theoretical investigation of X-Ray Absorption Spectroscopy (XAS) at the FeL2,3-edges and NK-edge. Results indicated that in this phase a mixed singlet/triplet state is plausible. These results have been compared with the already know Fe singlet spin state of the same complex in water solution. A detailed analysis of the electronic structure and bonding mechanism of the catalyst showed that the preference for the low-spin diamagnetic ground state, strongly depends upon the ligands, the bulk solvent and the interactio…

Reaction between Indazole and Pd-Bound Isocyanides-A Theoretical Mechanistic Study

The mechanism of the addition of indazole (Ind)&mdash

BUTENE/H-ZSM-5:STUDIO COMPUTAZIONALE DI MODELLI DI SUPERFICIE E CATALITICI.

Organotin IV-Quinilone Antibiotic Derivatives: Solid State Investigations

Synthesis, chemical characterization and preliminary in vitro antitumor activity evaluation of new ruthenium(II) complexes with sugar derivatives

Abstract Three new complexes of Ru(II), namely [RuCl 2 (Glun-N,O) 2 ]Na 2 ( I ; Glun = glucosaminate), [RuCl 2 (1-Tglu)(EtOH) 2 ]Na ( II ; 1-Tglu = 1-thio-β- d -glucose) and [Ru 2 (EtOH) 6 (AL)Cl 4 ] ( III ; AL = 6′-aminolactose) were prepared from the same Ru(II) precursor, [RuCl 2 (DMSO) 4 ] (DMSO = dimethyl sulfoxide). The characterization of the complexes was carried out by elemental analysis, FT-IR, ES-MS, NMR, EXAFS and DFT calculations. The effectiveness of the complexes on metastatic melanoma A 375 was investigated. The results show that complex II is the most active species.

Structural characterization of triorganotin(IV) complexes with sodium fusidate and DFT calculations

Abstract Three new complexes of the steroid sodium fusidate (sodium 2-[(1 S ,2 S ,5 R ,6 S ,7 S ,10 S ,11 S ,13 S , 14 Z ,15 R ,17 R )-13-(acetyloxy)-5,17-dihydroxy-2,6,10,11-tetramethyl tetracyclo[8.7.0.0 2,7 .0 11,15 ] heptadecan-14-ylidene]-6-methylhept-5-enoate = (NaFusidate, Na FA )]), with triorganotin(IV) moieties have been prepared and investigated by conventional techniques as FTIR, Mossbauer, ESI-MS and NMR spectroscopy. The isolated compounds showed stoichiometries organotin(IV)/fusidate 1/1, R 3 Sn(IV) FA (R = Me, FA1 ; Bu, FA2 ; Ph, FA3 ). The ligand coordination sites were determined by FTIR spectroscopic measurements. In the complexes, the carboxylate group of the fusidate li…

Equilibria involved in the diorganotin(IV) and triorganotin(IV) phosphomycin interaction in aqueous solution

Four new diorganotin(IV), (R = Me, Bu), and triorganotin(IV), (R = Me, Ph), derivatives of the phosphomycin disodium salt antibiotic[(1R,2S)-1,2-epoxypropylphosphonate]Na2 have been synthesized and their solid state configuration studied by X-ray crystallography, FT-IR, Mossbauer, UV–Vis spectroscopies. The X-ray diffraction investigation, performed on the bis[trimethyltin(IV)]- phosphomycin, showed that the coordination geometry at all the Sn atoms is trigonal bipyramidal. The structure of the complex forms an unusual polymeric zig-zag planar network. The FT-IR and the 119Sn Mo¨ssbauer studies supported the formation of trigonal bipyramidal (Tbp) molecular structures, both in the diorganot…

Solution structure of R2Sn(IV)-β-N-Acetyl-Neuraminate (R=Me, Bu) complexes in D2O and DMSO-d6: experimental NMR and DFT computational study.

Two diorganotin(IV)-NANA complexes (NANA (1) = beta-N-acetyl-Neuraminic Acid = 5-amino-3,5-dideoxy-D-glycero-beta-D-galactononulosic acid) with formula Me(2)Sn(iv)NANA (2) and Bu(2)Sn(IV)NANA (3) were synthesized and characterized by (1)H, (13)C and (119)Sn NMR spectroscopy, both in D(2)O and DMSO-d(6) solutions. The experimental data in DMSO suggested the monosaccharide bidentate chelation via O1 carboxylate and vicinal O2 alkoxide atoms, which, in D(2)O, can be dynamically extended to a third binding site (O8 atom) of the pendant chain. Coordination at the tin atom is discussed on the basis of experimental NMR data and DFT calculation.

Ionic liquid crystals based on viologen dimers: tuning the mesomorphism by varying the conformational freedom of the ionic layer

ABSTRACTWe investigated the liquid crystal behaviour of newly synthesised bistriflimide salts of symmetric viologen dimers. A smectic A phase was observed for intermediate spacer lengths and for relatively long lateral alkyl chains. The systems were characterised by thermal analysis, polarised optical microscopy, X-ray scattering and solid-state NMR. An intermediate ordered smectic phase was also exhibited by the compounds (except for systems with very short lateral chains) consisting of molten layers of alkyl chains and partially ordered ionic layers. These results, relating to the mesomorphic behaviour of viologen salts, are qualitatively compared to those of the more common imidazolium s…

119Sn NMR Ccomputational study of Dimethyltin(IV) - D-ribonic Acid and Dimethyltin(IV) - N-Acetylneuraminic acid complexes

Organotin(IV) derivatives of fatty acids: Solid state and solution phase investigations

How organotin(IV)(sulfonatophenyl) porphynate may activate the apoptotic pathways in melanoma cells?

Catalytic Supported System Modelled by Computational Approaches

Bu2Sn(N-acetyl-L-cysteinate) antitumor activity on HepG2 cells

Diorganotin(IV) N-acetyl-L-cysteinate complexes: synthesis, solid state, solution phase, DFT and biological investigations.

Diorganotin(IV) complexes of N-acetyl-L-cysteine (H(2)NAC; (R)-2-acetamido-3-sulfanylpropanoic acid) have been synthesized and their solid and solution-phase structural configurations investigated by FTIR, Mössbauer, (1)H, (13)C and (119)Sn NMR spectroscopy. FTIR results suggested that in R(2)Sn(IV)NAC (R = Me, Bu, Ph) complexes NAC(2-) behaves as dianionic tridentate ligand coordinating the tin(IV) atom, through ester-type carboxylate, acetate carbonyl oxygen atom and the deprotonated thiolate group. From (119)Sn Mössbauer spectroscopy it could be inferred that the tin atom is pentacoordinated, with equatorial R(2)Sn(IV) trigonal bipyramidal configuration. In DMSO-d(6) solution, NMR spectr…

Recent Results of Studies on Dialkyltin(IV) Complexes of Acidic Derivatives of Carbohydrates

Anti-cancer activity of di- and tri-organotin(IV) compounds with D-(+)-Galacturonic acid on human tumor cells

Abstract We have compared the anti-proliferative activity in vitro, of R2SnGala (1-3) [R = Me, n-Bu, Ph] and novel R3SnGala (4, 5) [R = Me, n-Bu] with D-(+)-Galacturonic acid [HGala; Galaq-, q = (2) and (1) for R2SnGala and R3SnGala, respectively] compounds, towards human tumor cell lines of intestinal carcinoma (HCT-116) and breast adenocarcinoma (MCF-7). The new synthesized 4 and 5 compounds were characterized, in solution, by 1H, 13C and 119Sn NMR, that showed that HGala acts as monoanionic moiety and evidenced the dynamic behavior of the compounds, due to inter-conversions involving the anomeric carbon atom of the ligand. Cell viability, apoptosis induction and cell cycle distribution w…

Organometallic complexes with biological molecules. XVIII. Alkyltin(IV) cephalexinate complexes: synthesis, solid state and solution phase investigations

Abstract Dialkyltin(IV) and trialkyltin(IV) complexes of the deacetoxycephalo-sporin-antibiotic cephalexin [7-( d -2-amino-2-phenylacetamido)-3-methyl-3-cephem-4-carboxylic acid] (Hceph) have been synthesized and investigated both in solid and solution phase. Analytical and thermogravimetric data supported the general formula Alk 2 SnOHceph · H 2 O and Alk 3 Snceph · H 2 O (Alk=Me, n -Bu), while structural information has been gained by FT-IR, 119 Sn Mossbauer and 1 H, 13 C, 119 Sn NMR data. In particular, IR results suggested polymeric structures both for Alk 2 SnOHceph · H 2 O and Alk 3 Snceph · H 2 O. Moreover, cephalexin appears to behave as monoanionic tridentate ligand coordinating th…

Comparative Experimental and Theoretical Study of the C and O K-Edge X-ray Absorption Spectroscopy in Three Highly Popular, Low Spin Organoiron Complexes: [Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]

The unoccupied electronic structures of three closed-shell, highly popular organoiron complexes ([Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]; 0, I, and II, respectively) have been investigated both experimentally and theoretically by combining original gas-phase X-ray absorption spectroscopy (XAS) outcomes recorded at the C and O K-edge with results of scalar relativistic time-dependent density functional calculations carried out within the zeroth order regular approximation. Experimental evidence herein discussed complement the Fe L2,3-edges XAS ones we recently recorded, modeled, and assigned for the same complexes (Carlotto et al. Inorg. Chem. 2019, 58, 5844). The first-princ…

Pt(II) nitrile complexes: New insights on old complexes from a combined experimental and theoretical study

Abstract The spectroscopic characterization of cis - and trans -[PtCl 2 (NCR) 2 ] (R = CH 3 , Ph, CH 2 Ph) was reported in solid state and solution phase. Moreover, the X-ray structures of cis -[PtCl 2 (NCCH 3 ) 2 ], cis - and trans -[PtCl 2 (NCPh) 2 ] were redetermined at low temperature. FT-IR and NMR showed a blue-shift and a slight shielding of the νCN and δ ( 13 C CN ) values, respectively, in a counterintuitive way with respect to the well known improved reactivity towards nucleophiles of nitriles ligands coordinated to platinum(II), when compared to their free forms. These spectroscopic behaviors were also confirmed by theoretical experiments at DFT level. Moreover, DFT approach show…

CO on Nickel: some computational insights about steric hindrance in loaded surfaces

Organotin(IV) and simple fatty acids: preliminary assessments

Our group has a long researching tradition in the field of organotin(IV) complexes, usually proposed and tested as potential anti-tumor drugs. The leitmotif has usually been the modulation of the intrinsic toxicity/cytotoxicity of the organometallic moiety and a modulation of the toxic effect by means of biologically related molecules (synthetic or natural). Such a modulation is usually achieved by two (often overlapping) routes: dampen the damaging effects of the metal core, and serving as a carrier for specific tissue districts. Since a too tight binding on the organotin moiety is not always desirable – a too much stable complex could be a non-active one – carboxylates have always played …

Relativistic DFT Calculation of (119)Sn Chemical Shifts and Coupling Constants in Tin Compounds.

The nuclear shielding and spin-spin coupling constants of (119)Sn in stannane, tetramethylstannane, methyltin halides Me4-nSnXn (X = Cl, Br, I; n = 1-3), tin halides, and some stannyl cations have been investigated computationally by DFT methods and Slater all-electron basis sets, including relativistic effects by means of the zeroth order regular approximation (ZORA) method up to spin-orbit coupling. Calculated (119)Sn chemical shifts generally correlate well with experimental values, except when several heavy halogen atoms, especially iodine, are bound to tin. In such cases, calculated chemical shifts are almost constant at the scalar (spin-free) ZORA level; only at the spin-orbit level i…

Viologen-based ionic liquid crystals: induction of a smectic A phase by dimerisation.

The stability of thermotropic ionic liquid crystals is essentially due to micro-phase segregation between the ionic heads and the long alkyl chains. Here we show, using newly synthesized viologen dimers, that the structure of the central core is another key parameter to play with in order to tune the mesomorphic behaviour. © 2014 the Owner Societies.

Through-space spin-spin coupling in acetylenic systems. Ab initio and DFT calculations

Abstract: We have investigated, by means of ab initio and DFT calculations, the magnitude of through-space spin-spin couplings ( J CH and J HH ) in CH/π bonded van der Waals dimers involving acetylene, and in a structurally related covalent compound (4-ethynylphenanthrene). Within regions where the interaction is stabilizing J HH couplings are very small (< 0.1 Hz) for all complexes. In the acetylene-methane complex J CH is also very small, whereas in the acetylene-benzene complex and the acetylene dimer it shows a relatively large dependence on the tilt angle from the T-shaped arrangement, for which the smallest values are calculated, to a parallel slipped arrangement where J CH is ca. 0.5…

DFT calculation of NMR δ(113Cd) in cadmium complexes

Abstract We have tested several DFT protocols, at the non-relativistic and relativistic ZORA (scalar and spin–orbit) levels, for the calculation of the 113Cd chemical shifts, δ(113Cd), for a number of cadmium complexes accounting for both different local coordination environments on the metal center, involving N, O and S ligands, and different geometrical arrangements. Moreover, suitable models as reference compounds for δ(113Cd) evaluation have been set up in order to propose a complete computational approach to calculate δ(113Cd) for cadmium complexes. Inclusion of relativistic corrections did not lead to any sensible improvement in the quality of results and, in this context, non-relativ…

cis-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2, the poor relative between cis and trans tautomers. A theoretical study of the gas-phase Fe L3-edge and C and O K-edge XAS of trans-/cis-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2

The relative stability of trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 (trans-I) and cis-I tautomers in a vacuum and in solvents with different dielectric constants (e) has been investigated by exploiting density functional theory (DFT). Theoretical results indicate that, in agreement with experimental evidence, trans-I is more stable than cis-I in a vacuum (∼1.5 kcal mol−1; e = 1), while the opposite is true in media with e > 7. Differently from solution, DFT outcomes pertaining to the vapor-phase cis-I ⇆ trans-I equilibrium at T = 368 K, the temperature at which the Fe L2,3-edges and the C and O K-edge X-ray absorption spectroscopy (XAS) data of I have been recorded, ultimately indicate the trans-I …

Direct detection of 17O NMR in [Gd(DOTA)]- by NMR Spectroscopy

The 17O NMR spectrum of the non-coordinated carboxyl oxygen in the GdIII-DOTA (DOTA = tetraazacyclododecanetetraacetic acid) complex has been observed experimentally. Its line width is essentially unaffected by paramagnetic relaxation due to gadolinium, and is only affected by the quadrupole pathway. The results are supported by the relevant parameters (hyperfine and quadrupole coupling constants) calculated by relativistic DFT methods. This finding opens up new avenues for investigating the structure and reactivity of paramagnetic GdIII complexes used as contrast agents in magnetic resonance imaging.

SIMPLE MODEL OF GERMANIUM-PEPTIDE INTERACTIONS: BIS-GLYCYLGLYCINE-GERMANIUM-CHLORIDE

Synthesis, characterization and in vitro antimicrobial activity of triorganotin(IV)fusidate complexes

Synthesis, structural investigations on organotin(IV) chlorin-e6 complexes, their effect on sea urchin embryonic development and induced apoptotic changes

Studi computazionali di proprietà catalitiche di zeoliti acide

DFT calculation of NMR delta(Cd-113) in cadmium complexes

We have tested several DFT protocols, at the non-relativistic and relativistic ZORA (scalar and spin–orbit) levels, for the calculation of the 113Cd chemical shifts, δ(113Cd), for a number of cadmium complexes accounting for both different local coordination environments on the metal center, involving N, O and S ligands, and different geometrical arrangements. Moreover, suitable models as reference compounds for δ(113Cd) evaluation have been set up in order to propose a complete computational approach to calculate δ(113Cd) for cadmium complexes. Inclusion of relativistic corrections did not lead to any sensible improvement in the quality of results and, in this context, non-relativistic met…

Donation and back-donation in cis- and trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 tautomers: Which relative is more generous? An ETS-NOCV bond analysis

The ETS-NOCV bond analysis has been exploited to quantitatively estimate donation and back-donation properties of [(η5-C5H5)]−, CO, and FeI in the cis-/trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 (cis-I/trans-I) tautomers. Theoretical outcomes indicate that the Fe-CO bond, regardless to the CO monoapto (η1-) or bridging (μ-) coordination, has a sizeable π Fe → CO back-bonding contribution, which is stronger in trans-I than in cis-I. Moreover, [(η5-C5H5)]− has the weakest back-donation acceptor capability. The back-bonding behaviour of the Fe → η1-CO interaction well agrees with the experimental symmetric/antisymmetric infrared νCO (sνηjavax.xml.bind.JAXBElement@fc12185-CO/aνηjavax.xml.bind.JAXBElemen…

A DFT study of the Karplus-type dependence of vicinal 3J(Sn-C-X- C), X=N,O,S, in organotin(iv) compounds: Application to conformationally flexible systems

ZORA relativistic and non-relativistic DFT protocols have been used to investigate vicinal coupling constants, (3)J(Sn-C-X-C), in several organotin(iv) compounds, with particular emphasis on cyclic alpha-aminoorganostannanes. The dependence of the coupling constant on the heteroatom X (X = N,O,S) in the coupling path, and, for X = N, its substituents, has been studied in detail. The electron-withdrawing strength of the N-substituents has been found to strongly affect the magnitude and shape of the Karplus-type curve. The results obtained for the simple model systems, having no or little conformational flexibility, have helped in rationalizing the data concerning real flexible cyclic systems…

Carbocysteine degradation catalyzed by organotin(IV) compounds.

Novel metallic and organometallic based antiproliferative complexes: Integrated methodologies of evaluation

Potential use of organotin(IV)-tripetide complexes as stopper in tumor cells growth.

Synthesis and structural investigations on R2Sn(IV)-D-aldonic acid complexes (R = methyl; butyl). Their effect on a new toxicity test organism,Liza saliens(Osteichthyes, Mugilidae): a histological study

Eight R2Sn(IV)-D-aldonate complexes [(R = Me, Bu; D-aldonate = D-galactonate2− (Galn), D-Gluconate2− (Glun), D-Gulonate2− (Guln), D-Ribonate2− (Ribn)], five of which are new derivatives, have been synthesized and structurally characterized both in solid and solution state by IR, 119Sn Mossbauer and 1H, 13C, 119Sn NMR spectroscopies, showing that ligands act as dianonic chelating agents. In solution phase, NMR data suggest that the bidentate chelation is attained by the O1 carboxylate and the vicinal O2 alkoxide atoms, which can be dynamically extended to a third binding site (O4) competing with O2. In Me2Sn(IV)-D-gluconate complex the occurrence of a self-association process leading to a di…

CONFORMATIONAL ANALYSIS AND DFT-GIAO 13CNMR CHEMICAL SHIFT CALCULATION OF DIMETHYLTIN(IV)-D-RIBONATE COMPLEX

Polyfluoroalkyl viologen-based Ionic Liquid Crystals

Synthesis, structural characterization and antitumor activity of di- and tri-organotin(IV) complexes of D-galacturonic acid

ATTIVITÀ CITOTOSSICA DEI COMPLESSI DIORGANOSTAGNO(IV)-N-ACETILCISTEINA SU CELLULE DI MELANOMA A-375.

An ultrathin suspended hydrophobic porous membrane for high-efficiency water desalination

Abstract An ultrathin highly fluorinated porous membrane was designed for a large production of desalted water at very low energy consumption. Imprinting water droplets were used through a low thermally conductive tetra-fluoroethylene (TFE)/2,2,4-trifluoro-5-tri-fluorometoxy-1,3-dioxol (TIT) (HYFLON AD 60) solution and the generated porous nanofilm was suspended onto a polyethersulfone (PES) honeycomb texture. The very tiny fluorinated thickness together with a large number of small-shaped pores provided the membrane for enhanced anti-wetting surface properties, extremely reduced resistance to water vapor transfer and outstanding thermal efficiency. Fine materials structure-transport relati…

Structural investigations on diorganotin and triorganotin(IV) phosphomycin derivatives.

Abstract Four new diorganotin(IV), (R = Me, Bu), and triorganotin(IV), (R = Me, Ph), derivatives of the phosphomycin disodium salt antibiotic[(1R,2S)-1,2-epoxypropylphosphonate]Na2 have been synthesized and their solid state configuration studied by X-ray crystallography, FT-IR, Mossbauer, UV–Vis spectroscopies. The X-ray diffraction investigation, performed on the bis[trimethyltin(IV)]phosphomycin, showed that the coordination geometry at all the Sn atoms is trigonal bipyramidal. The structure of the complex forms an unusual polymeric zig-zag planar network. The FT-IR and the 119Sn Mossbauer studies supported the formation of trigonal bipyramidal (Tbp) molecular structures, both in the dio…

Quantum chemical models of acidic sites in H-ZSM-5 zeolites

Four-Component Relativistic DFT Calculations of C-13 Chemical Shifts of Halogenated Natural Substances

We have calculated the (13) C NMR chemical shifts of a large ensemble of halogenated organic molecules (81 molecules for a total of 250 experimental (13) C NMR data at four different levels of theory), ranging from small rigid organic compounds, used to benchmark the performance of various levels of theory, to natural substances of marine origin with conformational degrees of freedom. Carbon atoms bonded to heavy halogen atoms, particularly bromine and iodine, are known to be rather challenging when it comes to the prediction of their chemical shifts by quantum methods, due to relativistic effects. In this paper, we have applied the state-of-the-art four-component relativistic density funct…

Karplus-Type Dependence of Vicinal119Sn-13C and119Sn-1H Spin-Spin Couplings in Organotin(IV) Derivatives: A DFT Study

The empirical Karplus-type dependence of (3)J((119)Sn,(13)C) and (3)J((119)Sn,(1)H) couplings in organotin(IV) derivatives has been computationally validated by DFT methods both at the nonrelativistic and scalar ZORA relativistic level. A preliminary calibration of the computational protocols, by comparing experimental and calculated couplings for a Set Of Suitable rigid molecules, revealed their high predictive power: in particular, relativistic results for (3)J((119)Sn,(13)C) have a mean absolute error of just above 2 Hz, over a range of values up to about 70 Hz. The latter protocol has then been used to study in detail the influence of substituents and multiple paths connecting the coupl…

Tin(IV) catalyzed D-galacturonic acid anomerization

A comparative kinetic study of anomerization between the four main forms (alpha/beta-pyranosides and alpha/beta-furanosides) of D-galacturonic acid (GalAH(2), 1) and tin(IV) complexed D-galacturonate ([Sn(CH(3))(2)(GalA)(H(2)O)(2)], 2) in D(2)O, is reported. Important differences are shown by pD vs. mutarotation rate profiles of 1 and 2. Coordination, in fact, causes: i) a spectacular increase of the rate due to kinetic template assistance of the carboxylic tail holding the metal in close proximity to the reactive centre and ii) a change in the dependence of the rate on the pD. Entropic and enthalpic factors contribute to the huge activation energy decrease in 2. Anomerization rates of the …

Recent results on DFT calculation of 119Sn NMR parameters for organotin(IV) derivatives in coordinating solvents

DFT calculation of 1J(119Sn,13C) and 2J(119Sn,1H) coupling constants in di- and trimethyltin(IV) compounds

We have tested several computational protocols, at the nonrelativistic DFT level of theory, for the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) spin-spin coupling constants in di- and trimethyltin(IV) derivatives with various ligands. Quite a good agreement with experimental data has been found with several hybrid functionals and a double-zeta basis set for a set of molecules comprising tetra-, penta-, and hexa-coordinated tin(IV). Then, some of the protocols have been applied to the calculation of the 2J(119Sn, 1H) of the aquodimethyltin(IV) ion and dimethyltin(IV) complex with D-ribonic acid and to the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) of the dimethyltin(IV)-glycylglycin…

Synthesis and characterization of diorganotin(IV)complexes with Phenothiazine class Drugs. Biological and Theoretical studies on cytotoxic activity

A novel compound of triphenyltin(IV) with N-tert-butoxycarbonyl-L-ornithine causes cancer cell death by inducing a p53-dependent activation of the mitochondrial pathway of apoptosis

The triphenyltin(IV) compound with N-tert-butoxycarbonyl-L-ornithine (Boc-Orn-OH), [Ph3Sn(Boc-Orn-O)], was synthesized and characterized by elemental analysis, FT-IR, solution1H,13C and119Sn NMR and ESI mass spectrometry. The organotin(IV) compound inhibited at very low micromolar concentrations the growth of human tumor cell lines HepG2 (hepatocarcinoma cells), MCF-7 (mammary cancer) and HCT116 (colorectal carcinoma) while it did not affect the viability of non-malignant human-derived hepatic cells Chang. The mechanism of the antiproliferative effect of Ph3Sn(Boc-Orn-O), investigated on human hepatoma HepG2 cells, was pro-apoptotic, being associated with externalization of plasma membrane …

Mesomorphic and electrooptical properties of viologens based on non-symmetric alkyl/polyfluoroalkyl functionalization and on an oxadiazolyl-extended bent core

Two different sets of ionic liquid crystals based on bistriflimide salts of non-symmetrically substituted polyfluorinated bipyridinium (viologens) and bent symmetrically substituted dialkyl-oxadiazolyl-bipyridinium have been synthesized, in order to study the effect on the mesomorphic and electrooptical properties of the non-symmetric functionalization (alkyl chain and fluoroalkyl chains of different lengths) on the two pyridinium rings and additionally the effect of a bent conjugated spacer among the two pyridinium units of the viologen. POM and DSC characterization show that the synthesized salts have a mesomorphic and, in some cases, polymesomorphic behaviour in a wide thermal range, als…

Diorganotin(IV) complexes with aldonic acids. Synthesis and structural study in solid state and in solution phase and biological activity

Cyclo- and Polyphosphazenes for Biomedical Applications

Cyclic and polyphosphazenes are extremely interesting and versatile substrates characterized by the presence of -P=N- repeating units. The chlorine atoms on the P atoms in the starting materials can be easily substituted with a variety of organic substituents, thus giving rise to a huge number of new materials for industrial applications. Their properties can be designed considering the number of repetitive units and the nature of the substituent groups, opening up to a number of peculiar properties, including the ability to give rise to supramolecular arrangements. We focused our attention on the extensive scientific literature concerning their biomedical applications: as antimicrobial age…

DFT study of but-2-ene isomerization on H-ZSM-5 modified catalyst

H−ZSM-5 Modified Zeolite:  Quantum Chemical Models of Acidic Sites

A ZSM-5 fragment, containing 52 tetrahedral moieties, each of them formed by one silicon or one aluminum atom surrounded by four oxygen atoms, was employed to model (52T systems) by quantum chemical calculations (i) the influence of the positions of the acidic sites on the energetics of 22 aluminum monosubstituted and bisubstituted 52T acidic zeolite (H-ZSM-5) systems and (ii) the local adsorption properties and acidic strength of the corresponding -OH sites. The energetics and the structural properties of simpler acid H-ZSM-5 systems containing only five Tetrahedral moieties (5T systems) were also modeled for comparison. B3LYP/6-31G(d,p) partial geometry optimization routines were performe…

Diorganotin(IV) complexes ofD-galacturonic acid: solid-state and solution-phase structural study

Three diorganotin(IV) complexes of D-galacturonic acid (H2GalA; R = Me, n-Bu, Ph), two of which are new derivatives (R = Me, Ph), have been synthesized and their solid-state and solution-phase investigated by IR, Mossbauer, 1H, 13C and 119Sn NMR spectroscopy. The FTIR data suggest that H2GalA, in the dialkyltin derivatives, behaves as a dianionic ligand, coordinating the tin(IV) atom through an ester-type carboxylate and deprotonated alcoholic hydroxo groups, whereas a bridging carboxylate occurs in the diphenyltin(IV) complex. Octahedral and trigonal bipyramidal local geometries on tin(IV) atoms are proposed for dialkyltin(IV)GalA and diphenyltin(IV)GalA complexes respectively on the basis…

Synthesis and crystal structure of [(PhenH)(PhenH2)][BiCl6] . 2H2O with different o-phenanthroline protonations.

The reaction between bismuthate oxide and phen (1,10-phenanthroline) in acid medium led to the isolation of the unusual [(PhenH)(PhenH2)][BiCl6] 2H2O derivative, which has been characterized by X-ray analysis and IR spectroscopy. The compound crystallizes in the triclinic space group P1 with a = 8.313(2), b = 9.349(2), c = 9.807(3) A, a = 86.39(3), B = 110.27(3) and y = 106.48(3)°. The crystal structure is made of [BiCl6] 3- anions and [(PhenHXPhenr2)]3+cations. A network of hydrogen bond interactions involving the two clathrated water molecules, the phenanthroline moiety and the chlorines characterizes the entire structure.

Organotin(IV)derivatives neurotoxicity and their modulation by Baclofen

Several new diorganotin(IV) and triorganotin(IV) complexes with 4-amino-3- (4-chloro phenyl)]-butanoic acid ( = Baclofen) have been synthesized and their structure investigated both in the solid state and in solution phase through spectroscopic methods (FT-IR, Mössbauer, 1H and 13C NMR). According to experimental analytical data, the stoichiometry of the complexes has been proposed as R2SnBac2 and R3SnBac, respectively for diorganotin(IV) and triorganotin(IV) baclofen complexes. (Baclofen = HBac; R = Me, Bu, Ph).

Spectroscopic signatures of the carbon buckyonions C60@C180 and C60@C240: a dispersion-corrected DFT study

We have investigated, using dispersion corrected DFT methods, the structure and the spectroscopic properties of carbon buckyonions C-60@C-180 and C-60@C-240. C-60, C-180 and C-240 showed a noticeable variation of their geometries in C-60@C-180 and C-60@C-240, upon encapsulation. Inclusion of the dispersion correction term in the calculations has a significant effect on the geometry. C-60@C-180 has a large positive interaction energy, while for C-60@C-240 a negative value is found indicating that only C-240 can easily accommodate C-60. In both cases dispersion interactions strongly contribute to the stabilization of the complexes. Vibrational frequencies, electronic transitions and NMR prope…

A DFT mechanistic study of the synthesis of trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl from addition of NH3 to trans-[PtIICl2(N CMe)2]

Abstract The reaction mechanism between trans-[PtIICl2(N CMe)2] and ammonia to give trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl has been studied at DFT level. Results showed that, in dichloromethane solution at 263.15 K, the chloride substitution by the ammonia on platinum is a process kinetically more favoured than the ammonia nucleophilic addition to the nitrile of about three orders of magnitude, and hence the nucleophilic addition reaction occurs after. Finally, both nucleophilic addition steps are geometrically driven to give products in the E configuration even if the final products were experimentally observed in the Z configuration. For trans-Z,Z-[PtIICl(NH3)(N CMe)2, the isomerizatio…

Covalently Conjugated Gold-Porphyrin Nanostructures

Gold nanoparticles show important electronic and optical properties, owing to their size, shape, and electronic structures. Indeed, gold nanoparticles containing no more than 30&ndash

A DFT study of the vicinal 3J(119Sn,13C) and 3J(119Sn,1H) coupling constants in trimethyl- and chlorodimethyl-stannyl propanoates.

Abstract We have tested the performance of DFT protocols, both at the Scalar relativistic ZORA and non-relativistic level of theory, for the calculation of the 3 J( 119 Sn, 13 C) and 3 J( 119 Sn, 1 H) vicinal couplings for a series of flexible organotin(IV) derivatives with formula XMe2SnCHRCHR′COOMe (X = Me, Cl; R, R′ = Me, Ph). A satisfactory agreement between experimental and calculated vicinal couplings has been obtained by taking into account the conformational behaviour of the compounds investigated. The protocols used, mainly the relativistic one, were found to give a correct picture of the populations and a sufficiently high overall performance in calculating the vicinal couplings, …

Synthesis, chemical characterization and biological activity of new histone acetylation/deacetylation specific inhibitors: a novel and potential approach to cancer therapy

Three new triorganotin(IV) complexes of valproic acid (vp1, Me3Sn-valproate; vp2, Bu3Sn-valproate; vp3, Ph3Sn-valproate) have been synthesized and investigated by spectroscopic and biological methods. An anionic, monodentate valproate ligand was observed, ester-like coordinating the tin atom on a tetra-coordinated, monomeric environment. The structures, though, can distort towards a penta-coordination, as a consequence of a long range O center dot center dot center dot Sn interaction. Crystallographic and NMR findings confirm this situation both in solid state and solution. Biological finding evidenced a clear cytotoxic action of the complexes in hepatocellular carcinoma cell cultures: one …

Synthesis, structural investigation and biological activity of new diorganotin(IV) N-acetylcysteine Complexes.

Synthesis, Characterization and in vitro antimicrobial activity of dialkyltin(IV)bis(fusidate) complexes.

The complexation of one steroid antibiotic of the fusidane family, sodium fusidate [sodium 2-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12, 13,15,16-dodeca hydro-1H-cyclopenta[a]phenanthren-7-ylidene)-6-methyl-hept-5-enoate = (Nafus)], by dialkyltin(IV) has been studied by conventional technique as FT-IR, Mössbauer and NMR spectroscopies. Analytical data supported the general formula Alk2Sn(IV)fus2 (Alk = Me, Bu). Infrared spectral data of the complexes imply the presence of both uni- and bidentate, ester-type and bridging carboxylate group, respectively. On the basis of FT-IR and 119Sn Mössbauer spectroscopy, in both Me2Sn(IV)fus2 and Bu2Sn(IV)fus2, trigonal bipyram…

Thermal behaviour and electrochemical properties of bis(trifluoromethanesulfonyl)amide and dodecatungstosilicate viologen dimers

We report the synthesis and characterization of dimeric viologen salts (1',1''-(alkane-1,n-diyl)bis(1-ethyl-4,4'-bipyridinium) with n = 4-10) with bis(trifluoromethanesulfonyl)amide (bistriflimide, Tf(2)N(-)) as a counteranion. For n = 4, 5 and 6, and for the nonylviologen cation (1,1'-dinonyl-4,4'-bipyridinium) we also prepared salts with the totally inorganic dodecatungstosilicate anion, SiW(12)O(40)(4-), featuring a poly-charged surface and nanosized dimensions. The materials have been characterized by means of calorimetric techniques, X-ray diffraction and solid state NMR and a comparison is made with analogous monomeric viologen salts exhibiting smectic mesophases. A strong odd-even ef…

Metodi quantomeccanici e Monte Carlo applicati a sistemi nanostrutturati

New histone acetylation/deacetylation specific inhibitors: a novel and potential approach to cancer therapy

The acetylation status of histones is regulated in eukaryotes by two kinds of enzymes, histone acetyltransferases (HATs) and histone deacetylases (HDACs), which are responsible for acetylation and deacetylation of lysines residues in N-terminal tails of histone.[1] Thus acetylation, together with phosphorylation and methylation of N-terminal tail of histones, are involved in regulating fundamental processes, such as proliferation and cell death.[2-3] Sodium butyrate, which belongs together with valproic acid to the class of short chain fatty acids, was the first HDAC inhibitor (HDACI) to be identified.[1] Organotin compounds have various influences on physical function including the hormone…

DFT study of the interaction free energy of p–p complexes of fullerenes with buckybowls and viologen dimers

We present a theoretical investigation, by means of DFT protocols, of the complexation thermodynamics of (i) complexes of C70 and C60 fullerenes with bowl-shaped hexabenzocoronene derivatives and (ii) complexes of C60 with viologen dimers. The recent functionals of the M06 family, accounting for p-p interactions to a good level of approximation, have been used to calculate the interaction free energies. For the former complexes, the good agreement between the calculated results and the experimental data confirms the reliability of the protocol used. On these grounds, we then checked the stability of a series of complexes of C60 with some viologen dimers, 1BPnBP1 (n = 6-9), where two N-methy…

Organometallic Complexes with Biological Molecules. Structural investigation of cis-diammineplatinum(II)-Porphyrin derivatives.

CCDC 830010: Experimental Crystal Structure Determination

Related Article: Ornella Pellerito, Cristina Prinzivalli, Elisabetta Foresti, Piera Sabatino, Michele Abbate, Girolamo Casella, Tiziana Fiore, Michelangelo Scopelliti, Claudia Pellerito, Michela Giuliano, Giulia Grasso, Lorenzo Pellerito|2013|J.Inorg.Biochem.|125|16|doi:10.1016/j.jinorgbio.2013.04.008