Exploring C-F···π Interactions: Synthesis, Characterization, and Surface Analysis of Copper ß-Diketone Complexes.

Synthesis and characterization of two novel copper ß-diketone complexes, where halogen bonds play a pivotal role in shaping their multifaceted structural landscape, have been done in the present study. This study employs X-ray diffraction, ultraviolet-visible (UV-vis) spectroscopy, and infrared (IR) spectroscopy to investigate two copper ß-diketone complexes, [Cu(L1)2(ttfa)2]·2CH3OH (1) and [Cu(L1)(dfpb)2] (2), where Httfa is 4,4,4-trifluoro-1-(thiophen-2-yl)butan-3,1-dione and Hdfpb is 4,4-difluoro-1-phenylbutane-1,3-dione. Complex 1 displays a halogen bond, which contributes to its uniqueness. The coordination sphere around the copper atoms was found to be octahedral for complex 1 and pyramid with a square base for complex 2. The study also extensively discusses the interactions present in these complexes. Hirshfeld surface analysis was employed to gain a more detailed understanding of these interactions, and the results showed that hydrogen-bond interactions contributed above 30% of the whole surface area in both complexes. Additionally, the halogen bond in complex 1 was found to contribute approximately 8% of the surface. Overall, this study provides valuable insights into the structural properties and interactions of copper ß-diketone complexes, which could have potential applications in various fields.

Taming the oxidative power of SeO(3) in 1,4-dioxane, isolation of two new isomers of mixed-valence selenium oxides, and two unprecedented cyclic esters of selenic acid.

The reaction of (SeO3)4 with 1,4-dioxane (diox, dioxane) with or without diluting solvent led to the isolation of the unprecedented esters of selenic acid-1,2-ethyl selenate (CH2O)2SeO2 and the glyoxal diselenate O2Se[(OCHO)2]SeO2. It was possible to isolate an unknown dimeric form of Se2O5 (Se4O10·(diox)2) and a geometrical isomer of the mixed-valence oxide trans-Se3O7, both stabilized by dioxane. The dioxane adduct of monomeric selenium trioxide SeO3·diox was obtained from the reaction of (SeO3)4 with dioxane in liquid SO2. The reaction mechanism for the formation of these compounds was elucidated, and the molecular structure of the unstable form of the selenium trioxide was determined, consisting in a trimeric arrangement (SeO3)3.

Peroxido complexes of vanadium(V) as ligands. Crystal structures of [Cd(NH3)6][{VO(O2)2(OH)}2{µ-Cd(NH3)4}] and [{VO(O2)2(Im)}2{µ-Cu(Im)4}] (Im = Imidazole).

Two novel heterometallic complexes [Cd(NH3)6][{VO(O2)2(OH)}2{µ-Cd(NH3)4}] (2) and [{VO(O2)2(Im)}2{µ-Cu(Im)4}] (3) (Im = imidazole) containing peroxidovanadium complexes as metalloligands were prepared and characterized by spectral methods. X-ray single-crystal analysis revealed the presence of unique trinuclear complexes in the crystal structures of 2 and 3. The structure of 2 contains an anionic complex, whose two {VO(O2)2(OH)}(2-) ions are interconnected by a {µ-Cd(NH3)4}(2+) group. Compound 3 is a trinuclear neutral complex comprising two {VO(O2)2(Im)}(-) ions and a single bridging {µ-Cu(Im)4}(2+) group. The bonding via an equatorial OH(-) ligand in 2 and via a doubly bonded apical oxygen atom in 3 represents coordination modes previously unobserved for diperoxidovanadium complexes. Compared with complex 2, density functional theory studies reported decreased Cu-µ-O bond orders and increased µ-O-V bond orders in 3, in accordance with the expected Jahn-Teller distortion of the latter complex.

Stereospecific formation of dinuclear vanadium(V) tartrato complexes.

The first dinuclear nonperoxido tartrato complexes of vanadium(V), (NMe(4))(2)[V(2)O(4)((2R,3R)-H(2)tart)(2)] x 6 H(2)O (1), (NMe(4))(2)[V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)] (2), (NEt(4))(2)[V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)] (3) (tart = tartrato(4-) = C(4)H(2)O(6)(4-)) have been prepared from water-ethanol medium and characterized by X-ray structure analysis and spectral methods. The formation of the complexes has been found to be stereospecific; the composition and structure of anions containing one or both enantiomers of the ligand are profoundly different. The structure of anions in 1-3 also differs significantly from the structure of other dinuclear vanadium(V) alpha-hydroxycarboxylato complexes, but, interestingly, the geometry of the [V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)](2-) ion resembles the structure of the [(VO)(2)((2R,3R)-tart)((2S,3S)-tart)](4-) ion which has a vanadium(IV) center. Using Raman and (51)V NMR spectroscopy the solvent dependent mutual transformations of [V(4)O(8)((2R,3R)-tart)(2)](4-) (V(4)L(2)-RR), [V(4)O(8)((2S,3S)-tart)(2)](4-) (V(4)L(2)-SS), [V(2)O(4)((2R,3R)-H(2)tart)(2)](2-) (V(2)L(2)-RR), [V(2)O(4)((2S,3S)-H(2)tart)(2)](2-) (V(2)L(2)-SS), and [V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)](2-) (V(2)L(2)-rac) have been established. In aqueous solution the following reactions take place; 2 V(2)L(2)-rac --> V(2)L(2)-RR + V(2)L(2)-SS followed by partial decomposition, V(2)L(2)-RR --> V(4)L(2)-RR + 2 L (V(2)L(2)-SS --> V(4)L(2)-SS + 2 L). On the other hand V(2)L(2)-rac is stable in CH(3)CN solution while V(2)L(2)-RR (V(2)L(2)-SS) decomposes into several species.

Sodium scandium diphosphate, NaScP(2)O(7), isotypic with α-NaTi(III)P(2)O(7).

Crystals of the title compound, NaScP(2)O(7), were grown by a flux method. The crystal structure is isotypic with those of α-NaTiP(2)O(7), NaYbP(2)O(7) and NaLuP(2)O(7), and is closely related to that of NaYP(2)O(7). The structural set-up consists of a three-dimensional framework of P(2)O(7) units that are corner-shared by ScO(6) octa-hedra, forming tunnels running parallel to [010]. The Na atoms are situated in the tunnels and are surrounded by nine O atoms in a distorted environment.

Hexakis[3-(aminocarbonyl)pyridinium] decavanadate(V) dihydrate.

The structure of the title compound, (C(6)H(7)N(2)O)(6)[V(10)O(28)].2H2O, at 120 (2) K has monoclinic (C2/c) symmetry. The asymmetric unit consists of one half-decavanadate anion of Ci symmetry, three cations and one water molecule. Each water molecule is hydrogen bonded to two decavanadate anions, thus forming a one-dimensional chain of anions. The three-dimensional supramolecular structure is formed by a network of N-H...O, O-H...O and C-H...O hydrogen bonds, in which the cations, anions and water molecules are involved, and by nonparallel-displaced pi-stacking interactions between pyridine rings. As a result of hydrogen bonding, the carboxamide groups of the cations are somewhat twisted from the pyridine ring plane.

Vanadium(V) tartrato complexes: speciation in the H3O+(OH-)/H2VO4-/(2R,3R)-tartrate system and X-ray crystal structures of Na4[V4O8(rac-tart)2].12H2O and (NEt4)4[V4O8((R,R)-tart)2].6H2O (tart = C4H2O6(4-)).

A study of the aqueous H3O+(OH-)/H2VO4-/(2R,3R)-tartrate system has been performed at 273 K in a 1.0 mol/L Na+(Cl-) ionic medium using 51V NMR spectroscopy. In this relatively complicated system, more than 12 different species were observed. Ligand concentration, vanadate concentration, and pH variation studies were carried out, particularly for the range of pH 5.8-8.0 and for pH 2.4. Chemical shifts, vanadium-ligand stoichiometry, and also composition and formation constants for some, but not all, species are given. Despite some reduction of vanadium(V) to vanadium(IV) in an acidic medium at pH approximately 2.4, the stoichiometries of the principal species in solution at this pH were determined. Electrospray ionization mass spectra for some solutions were obtained and were in accordance with the conclusions drawn from the speciation studies. A series of crystalline vanadium(V) tartrato complexes M4[V4O8(tart)2].aq were also prepared and characterized. X-ray diffraction studies of Na4[V4O8(rac-tart)2].12H2O (1) and (NEt4)4[V4O8((R,R)-tart)2].6H2O (2) revealed unique tetranuclear [V4O8(tart)2]4- ions for which the {V4O4} rings have boat conformations.

The polysulfonylamines bis(methylsulfonamido) sulfone and bis(trifluoromethylsulfonamido) sulfone.

Bis(methylsulfonamido) sulfone, C(2)H(8)N(2)O(6)S(3) or SO(2)(NHSO(2)CH(3))(2), was synthesized from imidobis(sulfonyl chloride), HN(SO(2)Cl)(2), and bis(trimethylsilyl)methane, CH(2)[Si(CH(3))(3)](2), in chlorotrimethylsilane solution. In the solid state, there are two independent molecules linked by two N-H...O hydrogen bridges into infinite chains parallel to the b axis. The central S atoms of the independent molecules each lie on a twofold axis. Bis(trifluoromethylsulfonamido) sulfone, C(2)H(2)F(6)N(2)O(6)S(3) or SO(2)(NHSO(2)CF(3))(2), was formed by the reaction of trichlorophosphazosulfuryl trifluoromethane, Cl(3)PNSO(2)CF(3), with fluorosulfonic acid, FSO(3)H. The molecules are connected by bifurcated N-H...O bridges into infinite layers parallel to the [001] plane. The central S atom lies on a twofold axis.

Platinum(IV) complex with adamantylamine as nonleaving amine group: synthesis, characterization, and in vitro antitumor activity against a panel of cisplatin-resistant cancer cell lines.

Procedure of the synthesis is described for new platinum(IV) drug LA-12 [(OC-6-43)-bis(acetato)(1-adamantylamine)amminedichloroplatinum(IV)]. The X-ray diffraction analysis shows that the structure is created by molecules with octahedral arrangement of ligands around a platinum atom and contains one H(2)O molecule that is not a part of the coordination sphere of platinum. This new drug is more reactive with glutathione than cisplatin and is lacking cross-resistance with cisplatin as proven on the panel of cancer cell lines.

Diphenyldichlorophosphonium trichloride-chlorine solvate 1:1, [PPh2Cl2]+Cl(3)(-).Cl2: an ionic form of diphenyltrichlorophosphorane. Crystal structures of [PPh2Cl2]+Cl(3)(-).Cl2 and [(PPh2Cl2)+]2[InCl5](2-).

An ionic form of diphenyltrichlorophosphorane, namely, diphenyldichlorophosphonium trichloride isolated as a dichlorine solvate (1), was obtained by treating PPh(2)Cl(3) with excess chlorine. The identity of this species was established by single-crystal X-ray analysis and (31)P, (1)H, and (35)Cl NMR and Raman spectra. Bis(diphenyldichlorophosphonium) pentachloroindate (2) was obtained by the reaction of diphenyltrichlorophosphorane with indium trichloride in dichloromethane for comparison purposes. Its identity was determined by (31)P NMR spectra and single-crystal X-ray analysis.