Cytotoxic homoleptic Ti(iv) compounds of ONO-type ligands: synthesis, structures and anti-cancer activity.

Eight Ti(iv) compounds 1-8, of the type [Ti(Ln)2] where Ln is a variously substituted dianionic tridentate acylhydrazone, were synthesized by reacting the appropriate hydrazide with 2-hydroxybenzaldehyde or 2'-hydroxyacetophenone and titanium(iv) tetra(isopropoxide) in a 2 : 2 : 1 molar ratio. The solid-state structures of 1-6 and 7·CH2Cl2 were deduced from the single crystal X-ray diffraction data, which indicated that each L2- ligand is fully deprotonated and coordinated to the Ti(iv) cation via the enolic oxygen, the imino nitrogen and the phenolic oxygen atoms (ONO donor set) in an enol tautomeric form, the metal assuming the distorted octahedral geometry. The structures of pro-ligands H2L3 and H2L5 are also reported. All complexes displayed high hydrolytic stability. In vitro cytotoxicity assays towards human ovarian A2780 and colon HT-29 cancer cell lines revealed the activity dependence on the acylhydrazone substituents, with electron-donating groups on the phenolato units enhancing the solubility and promoting cytotoxicity. The lead compound 5 of this study presents IC50 values of 2.5 ± 0.2 and 4.2 ± 0.6 µM for ovarian A2780 and colon HT-29 human cancer cells, respectively.

Triphenylstannyl((arylimino)methyl)benzoates with selective potency that induce G1 and G2/M cell cycle arrest and trigger apoptosis via ROS in human cervical cancer cells.

Metal complexes with organelle specificity and potent but selective cytotoxicity are highly desirable. A novel series of triphenylstannyl 4-((arylimino)methyl)benzoates (2-8) were obtained by the reactions of triphenylstannyl 4-formylbenzoate [Ph3Sn(L1)] 1 with primary aromatic amines. Two representative compounds (10, 11) were also synthesized by reacting aqua-triphenylstannyl 2-formylbenzoate [Ph3Sn(L9)(H2O)] (9) with aniline and p-fluoroaniline, respectively. These compounds were characterized by elemental analysis, IR and 1H, 13C and 119Sn NMR spectroscopy, as well as single-crystal X-ray diffraction for compounds 5, 7-11 and three pro-ligands. The in vitro cytotoxic activities of 1-11 were assessed using the MTT tetrazolium dye assay against HeLa (human cervical) and MDA-MB-231 (breast) cancer cells, with IC50 values revealing high activity. Compared to cisplatin, compounds 1-11 exhibited enhanced cytotoxic efficacy, indicating their potential as potent anticancer agents. Among these, 1 and 5 demonstrated maximum inhibition in HeLa cells, with negligible effect on normal human embryonic kidney (HEK) cells. The combined results of the DCFH-DA dye and Hoechst 33342/PI nuclear staining assays, along with flow cytometry analysis, show that they possess a dual mode of action: They induced apoptotic cell death, attributable to the tin-assisted generation of reactive oxygen species. Cell cycle analyses indicated that compounds 1 and 5 exhibit cell growth inhibition and may cause turbulences in the G1 and G2/M phases.

Triphenyltin(IV) benzoates with diazenyl/imino scaffold exhibiting remarkable apoptosis mediated by reactive oxygen species.

The cytotoxic potency of a series of triphenyltin(IV) compounds of general composition [Ph3Sn(Ln)] (1-6) has been probed in vitro employing MDA-MB-231 (human breast cancer) and HeLa (human cervical cancer) cell lines, where Ln=L1-3; isomeric 2/3/4-{(E)-2-[4-(dimethylamino)phenyl]diazenyl}benzoates and L4-6 are their corresponding isoelectronic imino analogues 2/3/4-[(E)-{[4-(dimethylamino)phenyl]methylidene}amino]benzoates. Compounds 1-6 have been characterized by elemental analysis and their spectroscopic properties were studied using IR and NMR (1H, 13C, 119Sn) techniques. The molecular structures of a pro-ligand 2-[(E)-{[4-(dimethylamino)phenyl]methylidene}amino]benzoic acid (HL4) and two representative molecules, Ph3Sn(L2) 2 and Ph3Sn(L5) 5, have been determined by X-ray crystallography. Structural analyses of 2 and 5 revealed distorted tetrahedral geometries within C3O donor sets owing to monodentate modes of coordination of the respective carboxylate ligands, close intramolecular Sn…O(carbonyl) interactions notwithstanding. Cytotoxic studies in vitro in MDA-MB-231 and HeLa cell lines revealed high activity, in sub-micromolar range, for all investigated compounds. Among these, 1 and 3 exhibited potent cytotoxicity most effectively towards MDA-MB-231 cells with a IC50 value of 1.19 and 1.44µM, respectively, whereas 5 showed remarkable activity towards HeLa cells with a IC50 value of 0.88µM, yet the series of compounds had minimal cytotoxic effect on normal HEK 293 (human embryonic kidney) cell line. The underlying investigation suggested that the compounds exert potent antitumor effect by elevating intracellular reactive oxygen species generation and cause delay in cell cycle by inhibiting cells at G2/M phase. The results presented herein suggest further development of this class of triphenyltin(IV) compounds-based drugs as potential anti-cancer therapies should be pursued.

New dibutyltin(IV) ladders: Syntheses, structures and, optimization and evaluation of cytotoxic potential employing A375 (melanoma) and HCT116 (colon carcinoma) cell lines in vitro.

Synthesis and spectroscopic properties of seven new dibutyltin(IV) compounds of 2-{(E)-4-hydroxy-3-[(E)-4-(aryl)iminomethyl]phenyldiazenyl}benzoic acids (LnHH'; n=2-8) with general formula {[Bu2Sn(LnH)]2O}2 (1-7) are reported. The compounds were characterized by elemental analysis and by UV-Visible, fluorescence, IR, 1H, 13C and 119Sn NMR spectroscopies. Solid state structures of dibutyltin(IV) compounds 1-3, 6 and 7 were accomplished from single crystal X-ray crystallography which reveal the common ladder-type structure with two endo- and two exo-Sn atoms. The redox properties of LnHH' (n=2-4, 7 and 8) and their diorganotin(IV) compounds 1-3, 6 and 7 were also investigated by cyclic voltammetry. In general, the dibutyltin(IV) derivatives exhibited significant in vitro cytotoxic potency towards A375 (melanoma) and HCT116 (colon carcinoma) cell lines as determined by several experiments, like Live and Dead assay, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) cell viability assay, LDH (lactate dehydrogenase), cleavage of caspases and PARP (poly(ADP-ribose)polymerase), and DNA fragmentation. Dibutyltin(IV) compounds increase cell death without cytolysis and decreases membrane fluidity, without interfering with p53. Among the dibutyltin(IV) compounds, compound 6 was found to be the most potent, with an IC50 value of 78nM. A mechanism of action for tumor cell death is proposed.

Synthesis, photophysical properties and structures of organotin-Schiff bases utilizing aromatic amino acid from the chiral pool and evaluation of the biological perspective of a triphenyltin compound.

Five new organotin(IV) complexes of compositions [Me2SnL1] (1), [Me2SnL2]n (2), [Me2SnL3] (3), [Ph3SnL1H]n (4) and [Ph3SnL3H] (5) (where L1=(2S)-2-((E)-((Z)-4-hydroxypent-3-en-2-ylidene)amino)-3-(1H-indol-3-yl)propanoate, L2=(2S)-(E)-2-((2-hydroxybenzylidene)amino)-3-(1H-indol-3-yl)propanoate and L3=(2S)-(E)-2-((1-(2-hydroxyphenyl)ethylidene)amino)-3-(1H-indol-3-yl)propanoate were synthesized and spectroscopically characterized. The crystal structures of 1-4 were determined. For the dimethyltin derivative 2, a polymeric chain structure was observed as a result of a long Sn∙∙∙O contact involving the exocyclic carbonyl oxygen-atom from the tridentate ligand of a neighboring Sn-complex unit. The tin atom in this complex has a distorted octahedral coordination geometry, in which the long Sn-O bond is almost trans to the tridentate ligand nitrogen-atom. In contrast, the dimethyltin(IV) complexes 1 and 3 displayed discrete monomeric structures where the tin atom has distorted trigonal-bipyramidal geometry with the two coordinating L oxygen atoms defining the axial positions. On the other hand, 4 is a chain polymer in the solid state. The ligand-bridged Sn atoms adopt a trans-Ph3SnO2 trigonal-bipyramidal configuration with equatorial phenyl groups. A carboxylato oxygen atom from one and the hydroxyl oxygen of the successive ligand in the chain occupy the axial positions. The solution structures were predicted by the use of 119Sn NMR chemical shifts. The photophysical properties of the complexes were investigated in the solid and in solution. The triphenyltin(IV) compound 4 was tested in detail ex vivo against A375 (human melanoma) cell line, exhibiting an IC50 value of 261nM to induce cell death as assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay without significant alteration of cytolysis as determined by lactate dehydrogenase (LDH) assay. Compound 4-mediated potent cell death was also determined by Live and Dead assay and caspase-mediated cleavage of poly-ADP ribose polymerase (PARP). Potent cell death activity was not observed in primary cells, like blood-derived peripheral mononuclear cells (PBMC). Compound 4 inhibited the diphenyl hexatriene (DPH) binding to cells and decreased the micro viscosity in a dose-dependent manner. Additionally, the ability of 4 and cyclodextrin (CD) to interact was determined by molecular modelling.

Different Complexation Behavior of P-Functionalized Ferrocene Derivatives Towards SnCl2 , SnCl4 and SnPh2 Cl2 : Auto-ionization and Redox-Type Reactions.

The novel phosphonyl-substituted ferrocene derivatives [Fe(η(5) -Cp)(η(5) -C5 H3 {P(O)(O-iPr)2 }2 -1,2)] (Fc(1,2) ) and [Fe{η(5) -C5 H4 P(O)(O-iPr)2 }2 ] (Fc(1,1') ) react with SnCl2 , SnCl4 , and SnPh2 Cl2 , giving the corresponding complexes [(Fc(1,2) )2 SnCl][SnCl3 ] (1), [{(Fc(1,1') )SnCl2 }n ] (2), [(Fc(1,1') )SnCl4 ] (3), [{(Fc(1,1') )SnPh2 Cl2 }n ] (4), and [(Fc(1,2) )SnCl4 ] (5), respectively. The compounds are characterized by elemental analyses, (1) H, (13) C, (31) P, (119) Sn NMR and IR spectroscopy, (31) P and (119) Sn CP-MAS NMR spectroscopy, cyclovoltammetry, electrospray ionization mass spectrometry, and single-crystal as well as powder X-ray diffraction analyses. The experimental work is accompanied by DFT calculations, which help to shed light on the origin for the different reaction behavior of Fc(1,1') and Fc(1,2) towards tin(II) chloride.

Oxygen transfer from an intramolecularly coordinated diaryltellurium oxide to acetonitrile. Formation and combined AIM and ELI-D analysis of a novel diaryltellurium acetimidate.

The reaction of the intramolecularly coordinated diaryltellurium(IV) oxide (8-Me2NC10H6)2TeO with acetonitrile proceeds with oxygen transfer and gives rise to the formation of the novel zwitterionic diaryltelluronium(IV) acetimidate (8-Me2NC10H6)2TeNC(O)CH3 (1) in 57% yield. Hydrolysis of 1 with hydrochloric acid affords acetamide and the previously known diarylhydroxytelluronium(IV) chloride [(8-Me2NC10H6)2Te(OH)]Cl.

Diarylhalotelluronium(IV) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents.

The stoichiometrically controlled halogenation of the intramolecularly coordinated diaryltelluride (8-Me2NC10H6)2Te using SO2Cl2, Br2 and I2 was studied. At an equimolar ratio, the diarylhalotelluronium cations [(8-Me2NC10H6)2TeX](+) (1, X = Cl; 2, X = Br; 3, X = I) formed and were isolated as 1·Cl(-)·H2O·1/2THF, 2·Br(-), and 3·I(-), respectively. When the same reactions were carried out in the presence of KPF6, 1·PF6(-) and 22·Br(-)·PF6(-) were obtained. The chlorination of (8-Me2NC10H6)2Te with an excess of SO2Cl2 occurred with a double electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the ortho- and para-positions) and afforded the diaryltellurium dichloride (5,7-Cl2-8-Me2NC10H4)2TeCl2 (4). The bromination of (8-Me2NC10H6)2Te with three equivalents of Br2 took place with a single electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the para-positions) and provided the diaryltellurium dibromide (5-Br-8-Me2NC10H5)2TeBr2 (5), while an excess of Br2 produced the diarylbromotelluronium cation [(5-Br-8-Me2NC10H5)2TeBr](+) (6) that was isolated as 6·Br3(-). The reaction of (8-Me2NC10H6)2Te with two or three equivalents of iodine provided 3·I3(-) and 3·I3(-)·I2, respectively. In the presence of water, 1·Cl(-)·H2O·1/2THF, 2·Br(-), 3·I(-) and 3·I3(-) hydrolyzed to give the previously known diarylhydroxytelluronium cation [(8-Me2NC10H6)2TeOH](+) (7) that was isolated as 7·Cl(-), 7·Br(-)·H2O·THF, 7·I(-) and 7·I3(-)·H2O, respectively. The molecular structures of 1-7 were investigated in the solid-state by (125)Te MAS NMR spectroscopy and X-ray crystallography and in solution by multinuclear NMR spectroscopy ((1)H, (13)C, (125)Te), electrospray mass spectrometry and conductivity measurements. The stabilization of cations 1-3 by the intramolecular coordination was estimated by DFT calculations at the B3PW91/TZ level of theory.

Molecular indium(III) phosphonates possessing ring and cage structures. synthesis and structural characterization of [In2(t-BuPO3H)4(phen)2Cl2] and [In3(C5H9PO3)2(C5H9PO3H)4(phen)3]·NO3·3.5H2O.

Two novel indium(III) phosphonates, [In2(t-BuPO3H)4(phen)2Cl2] (1) and [In3(C5H9PO3)2(C5H9PO3H)4(phen)3]·NO3·3.5H2O (2) with phen = 1,10-phenanthroline, have been synthesized by solvothermal reactions involving indium(III) salts and organophosphonic acids. 1 is a dinuclear compound where the two indium centers are bridged by a pair of isobidentate phosphonate ligands, [t-BuP(O)2OH](-), resulting in an eight-membered (In2P2O4) puckered ring. Compound 2 is trinuclear; the In3 platform is held together by two bicapping tripodal phosphonate ligands from the top and bottom of the indium plane. In addition, two bridging monoanionic phosphonate ligands serve to bind two pairs of indium centers. Both 1 and 2 also contain monodentate monoanionic phosphonate ligands. The solid-state MAS (31)P NMR spectrum of complex 1 shows two signals at 21.9 and 29.3 ppm. Compound 2 contains signal maxima at 25.8 and 28.9 ppm, with a shoulder at 31.5 ppm. Room temperature solid-state fluorescence spectra of 1 and 2 are characterized by strong emission bands at 385 nm (λex = 350 nm) and 395 nm (λex = 350 nm), respectively, which are red-shifted with respect to the emission of free phenanthroline.

Mesityltellurenyl cations stabilized by triphenylpnictogens [MesTe(EPh(3))](+) (E = P, As, Sb).

The homoleptic 1:1 Lewis pair (LP) complex [MesTe(TeMes2)]O3SCF3 (1) featuring the cation [MesTe(TeMes2)](+) (1a) was obtained by the reaction of Mes2Te with HO3SCF3. The reaction of 1 with Ph3E (E = P, As, Sb, Bi) proceeded with substitution of Mes2Te and provided the heteroleptic 1:1 LP complexes [MesTe(EPh3)]O3SCF3 (2, E = P; 3, E = As) and [MesTe(SbPh3)][Ph2Sb(O3SCF3)2] (4) featuring the cations [MesTe(EPh3)](+) (2a, E = P; 3a, E = As; 4a, E = Sb) and the anion [Ph2Sb(O3SCF3)2](-) (4b). In the reaction with Ph3Bi, the crude product contained the cation [MesTe(BiPh3)](+) (5a) and the anion [Ph2Bi(O3SCF3)2](-) (5b); however, the heteroleptic 1:1 LP complex [MesTe(BiPh3)][Ph2Bi(O3SCF3)2] (5) could not be isolated because of its limited stability. Instead, fractional crystallization furnished a large amount of Ph2BiO3SCF3 (6), which was also obtained by the reaction of Ph3Bi with HO3SCF3. The formation of the anions 4b and 5b involves a phenyl group migration from Ph3E (E = Sb, Bi) to the MesTe(+) cation and afforded MesTePh as the byproduct, which was identified in the mother liquor. The heteroleptic 1:1 LP complexes 2-4 were also obtained by the one-pot reaction of Mes2Te, Ph3E (E = P, As, Sb) and HO3SCF3. Compounds 1-4 and 6 were investigated by single-crystal X-ray diffraction. The molecular structures of 1a-4a were used for density functional theory calculations at the B3PW91/TZ level of theory and studied using natural bond order (NBO) analyses as well as real-space bonding descriptors derived from an atoms-in-molecules (AIM) analysis of the theoretically obtained electron density. Additionally, the electron localizability indicator (ELI-D) and the delocalization index are derived from the corresponding pair density.

An in vitro comparative assessment with a series of new triphenyltin(IV) 2-/4-[(E)-2-(aryl)-1-diazenyl]benzoates endowed with anticancer activities: structural modifications, analysis of efficacy and cytotoxicity involving human tumor cell lines.

Four new triphenyltin(IV) complexes of composition Ph(3)SnLH (where LH=2-/4-[(E)-2-(aryl)-1-diazenyl]benzoate) (1-4) were synthesized and characterized by spectroscopic (((1))H, ((13))C and ((119))Sn NMR, IR, ((119))Sn Mössbauer) techniques in combination with elemental analysis. The ((119))Sn NMR spectroscopic data indicate a tetrahedral coordination geometry in non-coordinating solvents. The crystal structures of three complexes, Ph(3)SnL((1))H (1), Ph(3)SnL((3))H (3), Ph(3)SnL((4))H (4), were determined. All display an essentially tetrahedral geometry with angles ranging from 93.50(8) to 124.5(2)°; ((119))Sn Mössbauer spectral data support this assignment. The cytotoxicity studies were performed with complexes 1-4, along with a previously reported complex (5) in vitro across a panel of human tumor cell lines viz., A498, EVSA-T, H226, IGROV, M19 MEL, MCF-7 and WIDR. The screening results were compared with the results from other related triphenyltin(IV) complexes (6-7) and tributyltin(IV) complexes (8-11) having 2-/4-[(E)-2-(aryl)-1-diazenyl]benzoates framework. In general, the complexes exhibit stronger cytotoxic activity. The results obtained for 1-3 are also comparable to those of its o-analogs i.e. 4-7, except 5, but the advantage is the former set of complexes demonstrated two folds more cytotoxic activity for the cell line MCF-7 with ID(50) values in the range 41-53 ng/ml. Undoubtedly, the cytotoxic results of complexes 1-3 are far superior to CDDP, 5-FU and ETO, and related tributyltin(IV) complexes 8-11. The quantitative structure-activity relationship (QSAR) studies for the cytotoxicity of triphenyltin(IV) complexes 1-7 and tributyltin(IV) complexes 8-11 is also discussed against a panel of human tumor cell lines.

Intramolecularly coordinated telluroxane clusters and polymers.

The stoichiometrically controlled chlorination of the diarylditelluride (8-Me(2) NC(10) H(6) Te)(2) with SO(2) Cl(2) afforded the aryltellurinyl chloride 8-Me(2) NC(10) H(6) TeCl (1) and the aryltellurium trichloride 8-Me(2) NC(10) H(6) TeCl(3) (2). Alternatively, 1 was obtained by the reaction of the aryltellurenyl diethyldithiacarbamate 8-Me(2) NC(10) H(6) Te(S(2) CNEt(2) ) with hydrochloric acid. The base hydrolysis of 2 provided the novel telluroxanes (8-Me(2) NC(10) H(6) Te)(2) OCl(4) (3), (8-Me(2) NC(10) H(6) Te)(6) O(5) Cl(8) (4), (8-Me(2) NC(10) H(6) Te)(6) O(8) Cl(2) (5), [(8-Me(2) NC(10) H(6) Te)(2) O(3) ](n) (6) and (8-Me(2) NC(10) H(6) Te)(6) O(8) (OH)(2) (7) depending on the reaction conditions applied. The reaction of 7 with ClTe(OiPr)(3) in the presence of water gave rise to the telluroxane (8-Me(2) NC(10) H(6) Te)(6) Te(2) O(12) Cl(2) (8). The crystal and molecular structures of 1-3 and 5-8 were determined by X-ray crystallography. The telluroxane clusters and polymers 6-8 hold potential as model compounds for alkali tellurite glasses (M(2) O)(x) (TeO(2) )(1-x) (M=Li, Na, K) for which no precise structural data are available.

Dibutyltin(IV) complexes containing arylazobenzoate ligands: chemistry, in vitro cytotoxic effects on human tumor cell lines and mode of interaction with some enzymes.

Dibutyltin(IV) complexes of composition Bu2Sn(LH)2, where LH is a carboxylate residue derived from 2-[(E)-(5-tert-butyl-2-hydroxyphenyl)diazenyl]benzoate (L¹H) with water molecule (1), 4-[(E)-(5-tert-butyl-2-hydroxyphenyl)diazenyl]benzoate (L²H) (2) and 4-[(E)-(4-hydroxy-5-methylphenyl)diazenyl]benzoate (L³H) (3), were synthesized and characterized by spectroscopic (¹H, ¹³C and ¹¹9Sn NMR, IR, ¹¹9Sn Mössbauer) techniques. A full characterization was accomplished from the crystal structure of complex 1. The molecular structures and geometries of the complexes (1a i.e. 1 without water molecule and 3) were fully optimized using the quantum mechanical method (PM6). Complexes 1 and 3 were found to exhibit stronger cytotoxic activity in vitro across a panel of human tumor cell lines viz., A498, EVSA-T, H226, IGROV, M19 MEL, MCF-7 and WIDR. Compound 3 is found to be four times superior for the A498, EVSA-T and MCF-7 cell lines than CCDP (cisplatin), and four, eight and sixteen times superior for the A498, H226 and MCF-7 cell lines, respectively, compared to ETO (etoposide). The mechanistic role of cytotoxic activity of test compounds is discussed in relation to the theoretical results of docking studies with some key enzymes such as ribonucleotide reductase, thymidylate synthase, thymidylate phosphorylase and topoisomerase II associated with the propagation of cancer.

Molecular basis of the interaction of novel tributyltin(IV) 2/4-[(E)-2-(aryl)-1-diazenyl]benzoates endowed with an improved cytotoxic profile: synthesis, structure, biological efficacy and QSAR studies.

A series of tributyltin(IV) complexes based on 2/4-[(E)-2-(aryl)-1-diazenyl]benzoate ligands was synthesized, wherein the position of the carboxylate and aryl substituents (methyl, tert-butyl and hydroxyl) varies. The complexes, Bu(3)SnL(1-4)H (1-4), have been structurally characterized by elemental analysis and IR, NMR ((1)H, (13)C, and (119)Sn) and (119)Sn Mössbauer spectroscopy. All have a tetrahedral geometry in solution and a trigonal bipyramidal geometry in the solid-state, except for Bu(3)SnL(4)H (4) that was ascertained to have tetrahedral coordination by X-ray crystallography. Cytotoxicity studies were carried out on human tumor cell lines A498 (renal cancer), EVSA-T (mammary cancer), H226 (non-small-cell lung cancer), IGROV (ovarian cancer), M19 MEL (melanoma), MCF-7 (mammary cancer) and WIDR (colon cancer). Compared to cisplatin, test compounds 1-4 had remarkably good activity, despite the presence of substantial steric bulk due to Sn-Bu ligands. The quantitative structure-activity relationship (QSAR) studies for the cytotoxicity of organotin(IV) benzoates, along with some reference drug molecules, is also discussed against a panel of human tumor cell lines. Molecular structures of the tributyltin(IV) complexes (1-4) were fully optimized using the PM6 semi-empirical method and docking studies performed with key enzymes associated with the propagation of cancer, namely ribonucleotide reductase, thymidylate synthase, thymidylate phosphorylase and topoisomerase II. The theoretical results are discussed in relation to the mechanistic role of the cytotoxic active test compounds (1-4).

Amidomethylation of elemental tellurium: synthesis and solid state structures of N-substituted amidomethyltellurium(IV & II) derivatives.

Amidomethylation of Te(0) (elemental tellurium) as well as Te(II) (aryltellurium bromide, in situ) proceeds readily under mild conditions. It involves oxidative insertion of low valent tellurium into the C-Br bond of N-substituted alpha-bromoacetamides and provides a direct synthetic route to the stable, crystalline amidomethyltellurium(IV) dibromides, (RR'NCOCH(2))(2)TeBr(2) (RR'N = Et(2)N (1b), MePhN (2b), Me(c-Hex)N (3b), O(CH(2)CH(2))(2)N (4b)) and (Et(2)NCOCH(2))ArTeBr(2) (Ar = mesityl, 5b; 1-naphthyl, 6b). Biphasic bisulfite reduction of the dialkyltellurium dibromides afforded yellow to orange coloured amido functionalized symmetrical telluroethers, (RR'NCOCH(2))(2)Te (RR'N = Et(2)N (1), MePhN (2), Me(c-Hex)N (3), O(CH(2)CH(2))(2)N (4)), of which compound 2 was isolated as a crystalline solid. Oxidation of the new dialkyltelluroethers with dihalogens (Br(2), I(2)) or SO(2)Cl(2) afforded the corresponding amidomethyltellurium(IV) dihalides, (RR'NCOCH(2))(2)TeX(2) (RR'N = Et(2)N, X = Cl (1a), Br (1b), I (1c); RR'N = MePhN, X = Cl (2a), Br (2b), I (2c); RR'N = Me(c-Hex)N, X = Cl (3a), Br (3b), I (3c); RR'N = O(CH(2)CH(2))(2)N, X = Cl (4a), Br (4b), I (4c)) that were characterized by elemental analyses and multinuclear ((1)H, (13)C, (125)Te) NMR. Single crystal X-ray data on 1b, 1c, 2, 2b, 2c, 4b, 5b and 6b suggest that the N-substituted amidomethyl group acts as a small-bite chelating ligand, via intramolecular 1,4-Te...O coordination, towards the Te(IV) centre. Steric congestion around Te(IV) due to intramolecular secondary bonding interaction(s), reduced electrophilicity of Te(II) and the partial positive charge on N due to the resonating character of the amido group presumably prevents these atoms from participating in the intermolecular associative forces in the solid state. Instead, weak C-H...O and C-H...X H-bonding interactions take centre-stage in the self assembly.

New insights into the formation and reactivity of molecular organostannonic acids.

The controlled base hydrolysis of 2,6-Mes(2)C(6)H(3)SnCl(3) (1; Mes=mesityl) provided 2,6-Mes(2)C(6)H(3)Sn(OH)Cl(2).H(2)O (2) and the trinuclear organostannonic acid trans-[2,6-Mes(2)C(6)H(3)Sn(O)OH](3) (3), respectively. In moist C(6)D(6), 3 reversibly reacts with water to give the monomeric organostannonic acid 2,6-Mes(2)C(6)H(3)Sn(OH)(3) (3 a). The reaction of 3 with (tBu(2)SnO)(3), Ph(2)PO(2)H, and NaH, gives rise to the multinuclear hypercoordinated organostannoxane clusters [tBu(2)Sn(OH)OSnR(OH)(2)OC(OSntBu(2)OH)(2)(O)SnR(OH)(H(2)O)](2) (5), [RSn(OH)(2)(O(2)PPh(2))](2) (6), and Na(3)(RSn)(4)O(6)(OH)(3) (7), respectively (R=2,6-Mes(2)C(6)H(3)). The characterization of the new compounds is achieved by multinuclear NMR spectroscopy and electrospray mass spectrometry in solution and (119)Sn MAS NMR spectroscopy, IR spectroscopy, and X-ray crystallography in the solid-state.

Acylmethyl(aryl)tellurium(IV,II) derivatives: intramolecular secondary bonding and steric rigidity.

Electrophilic substitution of acylmethanes (methyl ketones), RCOCH3 (R = i-Pr, 1; Et, 2; Me, 3) with aryltellurium trichlorides, ArTeCl3 (Ar = 1-C10H7, Np, A; 2,4,6-Me3C6H2, Mes, B; 4-MeOC6H4, Anisyl, C) under mild conditions affords the corresponding acylmethyl(aryl)tellurium dichlorides (RCOCH2)ArTeCl2. Reduction of the dichlorides, gives tellurides, (i-PrCOCH2)ArTe, 1A-1C, which give the corresponding dihalides, (i-PrCOCH2)ArTeX2 (X = Cl, 1Aa-1Ca; Br, 1Ab-1Cb; I, 1Ac-1Cc) when reacted in situ with SO2Cl2, Br2 or I2. The unsymmetric tellurides are labile towards disproportionation and attempts to obtain them lead to the isolation of Ar2Te2 except in the case of (i-PrCOCH2)MesTe (1B), which represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellurium(IV) derivatives show separate 1H and 13C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands. The telluride, 1B with free rotation about Te-C(mesityl) bond shows, like the unsymmetric diorganotellurium(IV) dihalides, only one 125Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV) compounds is inferred from the X-ray diffraction data for 1Aa, 1Ac, 1Ba, 1Bb, 1cA and 1Cc which are indicative of the presence of intramolecular Te...O secondary bonding interactions (SBIs) at least in the solid state. As a consequence, steric repulsion in case of the mesityltellurium(IV) derivatives, 1Ba and 1Bb, reaches the threshold so as to cause loss of two-fold rotational symmetry of the mesityl group about the Te-C(mesityl) bond axis. Intermolecular C-HO...O H-bonding interactions appears to stabilize such an orientation of the aryl ligand at least in the solid state.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. Synthesis, characterization, and XRPD structures of [Sn(pcp)] and [Cu(pcp)].

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp=CH2(PhPO2)2(2-), have been synthesized and structurally characterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H2pcp) in water with SnCl2.2H2O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H2pcp acid and Cu(O2CMe)2.H2O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2(1)/c, a=11.2851(1), b=15.4495(6), c=8.6830(1) A, beta=107.546(1) degrees, V=1443.44(9) A, Z=4. Crystal data for [Cu(pcp)]: triclinic, space group P, a=10.7126(4), b=13.0719(4), c=4.9272(3) A, alpha=92.067(5), beta=95.902(7), gamma=87.847(4) degrees, V=685.47(7), Z=2. The tin compound has been characterized by 119Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.