Efficient Functionalization of Organosulfones via Photoredox Catalysis: Direct Incorporation of α-Carbonyl Alkyl Side Chains into α-Allyl-ß-Ketosulfones.

A novel and efficient method for functionalizing organosulfones has been established, utilizing a visible-light-driven intermolecular radical cascade cyclization of α-allyl-ß-ketosulfones. This process employs fac-Ir(ppy)3 as the photoredox catalyst and α-carbonyl alkyl bromide as the oxidizing agent. Via this approach, the substrates experience intermolecular addition of α-carbonyl alkyl radicals to the alkene bonds, initiating a sequence of C-C bond formations that culminate in the production of organosulfone derivatives. Notably, this technique features gentle reaction conditions and an exceptional compatibility with a wide array of functional groups, making it a versatile and valuable addition to the field of organic synthesis.

Visible-Light-Induced Difunctionalization of Alkenyl Ketones with α-Carbonyl Alkyl Bromide: Concomitant Installation of C-C Bonds.

The visible-light-promoted difunctionalization of alkenyl ketones has been developed for easy access of various tetralones, cyclopropane, or alkenyl migration compounds. With fac-[Ir(ppy)3] as the photocatalyst, alkenyl ketones captured the α-carbonyl alkyl radical and evolved through intramolecular cyclization and the elimination of a proton to give the difunctionalized products. This strategy is characterized by good yields, mild reaction conditions, and outstanding functional group tolerance.

Di-, tri- and tetraphosphine-substituted Fe/Se carbonyls: synthesis, characterization and electrochemical properties.

The active sites of [FeFe]-hydrogenase promoted by Fe/E (E = S, Se) clusters have attracted considerable interest due to their significance in understanding the interconversion of hydrogen with protons and electrons. As an extension of the study on Fe/Se clusters related to H-cluster model compounds of [FeFe]-hydrogenase, a series of tertiary phosphine substituted Fe/Se carbonyls were successfully prepared. The treatment of Fe2(µ-SePh)2(CO)6 (A) and excess PR3 resulted in the ferrous bis(selenolate) carbonyls Fe(SePh)2(CO)2(PR3)2 (PR3 = PPhMe2, 1; PMe3, 2) in moderate yields. In striking contrast, the reaction of Fe2(µ-SeCH2Ph)2(CO)6 (B) with the same PR3 ligand resulted in the PR3-disubstituted models Fe2(µ-SeCH2Ph)2(CO)4(PR3)2 (PR3 = PPhMe2, 3; PMe3, 4) as the principal products. The more interesting finding is that two independent isomers (anti- and syn-) can be isolated according to different reaction temperatures. Further reactions of 3 or 4 with PR3 under UV irradiation afforded the first PR3-trisubstituted 2Fe2Se derivatives Fe2(µ-SeCH2Ph)2(CO)3(PR3)3 (PR3 = PPhMe2, 5; PMe3, 6). 6 could be further converted into the tetrasubstituted product Fe2(µ-SeCH2Ph)2(CO)2(PMe3)4 (7), while no further substitution was observed with 5 and excess of PPhMe2. All the prepared compounds were fully characterized by elemental analysis, various spectroscopic techniques and X-ray crystallography. In addition, some electrochemical properties of these models were studied by cyclic voltammetry (CV) in MeCN. Compounds 4, 6 and 7 were found to be catalysts for the H2 evolution reaction under electrochemical conditions.

catena-Poly[[triphenyl-tin(IV)]-µ-3-methyl-phenyl-seleninato-κO:O'].

In the polymeric title coordination compound, [Sn(C(6)H(5))(3)(C(7)H(7)O(2)Se)](n), the Sn(IV) atom has a distorted trigonal-bipyramidal geometry, with two O atoms from two symmetry-related bridging seleninate ligands in axial positions and three phenyl groups in the equatorial plane. In the crystal, the complex exhibits a zigzag chain structure running parallel to the c axis. An intra-chain C-H⋯O hydrogen bond is observed.

catena-Poly[[trimethyl-tin(IV)]-µ-5-methyl-thio-phene-2-carboxyl-ato-κO:O'].

In the title polymeric coordination compound, [Sn(CH(3))(3)(C(6)H(5)O(2)S)](n), which contains two formula units in the asymmetric unit, the Sn(IV) atom has a distorted trigonal-bipyramidal geometry, with two O atoms of the ligands in axial positions and three methyl groups in equatorial positions. Adjacent Sn(IV) atoms are bridged by the ligands, thereby forming a chain propagating in [010].

catena-Poly[[trimethyl-tin(IV)]-µ-phenyl-seleninato-κO:O'].

In the title polymeric coordination compound, [Sn(CH(3))(3)(C(6)H(5)O(2)Se)](n), the Sn(IV) atom has a distorted trigonal-bipyramidal geometry, with two O atoms of two symmetry-related bridging phenyl-seleninate anions in axial positions and three methyl groups in equatorial positions. In the crystal, the complex exhibits a chain structure parallel to the b axis.

catena-Poly[[chloridodimethyl-tin(IV)]-µ-chloro-acetato-κO:O'].

In the title polymeric coordination compound, [Sn(CH(3))(2)(C(2)H(2)ClO(2))Cl](n), the Sn atom has a distorted trigonal-bipyramidal geometry, with two O atoms of the ligands in axial positions and two methyl groups and one Cl atom in equatorial positions. Adjacent Sn atoms are bridged by the two O atoms of the carboxylate ligand, forming a chain structure along the a-axis direction.

A water-stable multi-responsive luminescent Zn-MOF sensor for detecting TNP, NZF and Cr2O72- in aqueous media.

The wide prevalence of organic and inorganic pollutants in water from various industries is responsible for serious environmental problems and endangers human beings. Therefore, the search for effective methods to detect these pollutants has gained great importance. In this work, a new luminescent MOF, {[Zn(L)(bpe)0.5]·DMF}n (1) [H2L = 4,4'-((naphthalene-1,4-dicarbonyl)bis(azanediyl))dibenzoic acid, bpe = 1,2-bis(4-pyridyl)ethene], was solvothermally synthesized and structurally characterized. In this MOF, Zn-SBUs (SBUs = secondary building units) were connected by acylamide-containing dicarboxylate L2- and nitrogen-containing bpe molecules to yield a 3D porous framework with isolated DMF molecules in the pores. The activated solvent-free MOF sample (denoted as 1a) with good water-stability was obtained by the solvent-exchange and vacuum heat treatment techniques. The luminescence sensing experiments showed that 1a could sensitively, selectively and reversibly detect 2,4,6-trinitrophenol (TNP), nitrofurazone (NZF) and Cr2O72- in aqueous media, and the corresponding luminescence quenching mechanism has also been discussed. In addition, MOF 1a could quantitatively detect TNP, NZF and Cr2O72- in tap water samples, indicating that MOF 1a has the potential to detect the aforesaid pollutants in various environmental water matrices.

catena-Poly[[trimethyl-tin(IV)]-µ-2-phenyl-butano-ato].

In the title polymeric coordination compound, [Sn(CH(3))(3)(C(10)H(11)O(2))](n), the Sn atom has a distorted trigonal-bipyramidal coordination geometry, with two O atoms of two symmetry-related carboxyl-ate ligands in axial positions and three methyl groups in equatorial positions. In the crystal structure, carboxyl-ate bridges link the metal atoms, forming zigzag chains parallel to the b axis.

(µ-2,3-Dihydroxy-butane-1,4-dithiol-ato)bis-[triphenyl-tin(IV)].

In the title compound, [Sn(2)(C(6)H(5))(6)(C(4)H(8)O(2)S(2))], the geometry around the Sn atoms is distorted tetra-hedral. The hydr-oxy groups are involved in O-H⋯O hydrogen bonding, which connects mol-ecules into centrosymmetric dimers.

Bis(4,6-dimethyl-pyrimidine-2-thiol-ato)dimethyl-tin(IV).

The asymmetric unit of the title complex, [Sn(CH(3))(2)(C(6)H(7)N(2)S)(2)], contains two independent mol-ecules with similar configurations. In each, the Sn(IV) cation is coordinated by two methyl and two 4,6-dimethyl-pyrimidine-2-thiol-ate anions in a distorted SnS(2)C(2) tetra-hedral geometry. In the two mol-ecules, the S-Sn-S bond angles are 87.70 (5) and 88.93 (4)°, while the C-Sn-C bond angles are 125.7 (3) and 125.9 (2)°. Weak C-H⋯N hydrogen bonding is present in the crystal structure.

Novel triorganotin complexes based on phosphonic acid ligands: Syntheses, structures and in vitro cytostatic activity.

Six novel organotin phosphonate complexes, [(Me3Sn)4(HL1)4]n1, [(Me3Sn)2(HL2)2]n2, [(Me3Sn)2L3(H2O)]n3, [(Ph3Sn)(HL1)]64, [(Ph3Sn)2L2]n5 and [(Ph3Sn)2L3]66, derived from phosphonic acid ligands [NaHL1 = 1-C10H7OPO2(OH)Na, H2L2 = 1-C10H7PO(OH)2, H2L3 = 2-C10H7PO(OH)2], have been synthesized and characterized by elemental analysis, FT-IR, NMR (1H, 13C, 31P and 119Sn) spectroscopy and X-ray crystallography. The structural analysis reveals that complexes 1 and 5 display 1D infinite zig-zag chain structures, and complex 2 shows 1D right-handed helical chain structure, while complex 3 displays 1D left-handed helical chain structure. Complexes 4 and 6 are 24-membered macrocyclic rings interconnected by P, O and Sn atoms. Additionally, the molecules of complexes 1 and 3 are further linked through intermolecular π···π and O-H···O interaction into supramolecular structures, respectively. Furthermore, we preliminarily estimated in vitro cytostatic activity of complexes 1-6 against the human cervix tumor cells (HeLa), human hepatocellular carcinoma cells (HepG-2) and human normal breast cells (HBL-100). Importantly, the anti-proliferative properties and possible pathway of complex 6 are investigated, and the results demonstrate that complex 6 could induce apoptotic cell death via an overload of intracellular reactive oxygen species (ROS) levels and the dysfunctional depolarization of mitochondrial membranes.

catena-Poly[[trimethyl-tin(IV)]-µ-(1,1'-binaphthyl-2,2'-diyl phospho-nato)].

In the title polymeric coordination compound, [Sn(CH(3))(3)(C(20)H(12)O(4)P)](n), the Sn atom exhibits a distorted trigonal-bipyramidal coordination geometry with the phosphate O atoms of the 1,1'-binaphthyl-2,2'-diyl phospho-nate ligands in axial positions and equatorial sites occupied by the three methyl groups. Adjacent Sn atoms are bridged by coordination to the two O atoms of each 1,1'-binaphthyl-2,2'-diyl phospho-nate ligand, forming a one-dimensional chain structure parallel to the b axis.

catena-Poly[[trimethyl-tin(IV)]-µ-cyclo-hex-3-ene-1-carboxyl-ato].

The title compound, [Sn(CH(3))(3)(C(7)H(9)O(2))](n), forms an extended zigzag chain structure propagating parallel to [010]. The Sn atom is in a slightly distorted trigonal-bipyramidal coordination environment with two carboxyl-ate O atoms in the axial and the three methyl groups in equatorial sites. The cyclo-hexene ring has a distorted half-boat conformation. There is an intra-molecular C-H⋯O hydrogen bond.

catena-Poly[[dimethyl-tin(IV)]-µ-cis-cyclo-hexane-1,2-dicarboxyl-ato].

The title complex, [Sn(CH(3))(2)(C(8)H(10)O(4))](n), was synthesized from cis-cyclo-hexane-1,2-dicarboxylic acid and dimethyl-tin dichloride. The complex has a bridging bis-bidentate carboxyl-ate group resulting in a zig-zag chain structure parallel to [001]. The Sn atom is six-coordinated and displays a distorted octa-hedral geometry.

Dibutyl 2,2'-bipyridine-4,4'-dicarboxyl-ate.

In the title compound, C(20)H(24)N(2)O(4), the mol-ecule lies on a centre of symmetry and is approximately planar (r.m.s. deviation= 0.013 Šfor 26 non-H atoms). The carboxyl-ate group is inclined slightly to the neighbouring pyridine ring, forming a dihedral angle of 4.37 (2)°. The mol-ecules form stacks with an inter-planar separation of 3.547 (1) Å.

Dimethyl-bis(3-methylsulfanyl-1,2,4-thia-diazole-5-thiol-ato)tin(IV).

In the title compound, [Sn(CH(3))(2)(C(3)H(3)N(2)S(3))(2)], the Sn(IV) atom is coordinated within a C(2)N(2)S(2) donor set that defines a skew-trapezoidal bipyramidal geometry in which the methyl groups lie over the weakly coordinated N atoms. Two independent mol-ecules comprise the asymmetric unit, each of which lies on a mirror plane that passes through the C(2)Sn unit.

catena-Poly[[(3-methyl-sulfanyl-1,2,4-thia-diazole-5-thiol-ato)sodium]di-µ-aqua-κO:O].

The crystal structure of the title compound, [Na(C(3)H(3)N(2)S(3))(H(2)O)(2)](n), features polymeric chains made up of O⋯O edge-shared NaSN(H(2)O)(4) units running along the b axis. The Na(+) ion and all non-H atoms of the thia-diazole ligand lie on a mirror plane.

Self-assembly and characterization of a novel 2D network polymer containing a 60-membered organotin macrocycle.

The reaction of 1-(4-carboxyphenyl)-5-mercapto-1 H-tetrazole with trimethyltin chloride in the presence of sodium ethoxide in benzene affords a novel 2D organotin network structure complex 1, which is an unusual organotin network containing a hexanuclear 60-membered organotin macrocycle. The complex has been characterized by elemental analysis, IR, and (1)H, (13)C, and (119)Sn NMR spectroscopy. Furthermore, we have also characterized the complex by X-ray crystallography.

A novel octa-nuclear 32-membered zirconocene macrocycle based on the aromatic selenite.

A novel macrocyclic zirconocene(iv) aromatic selenite [(CpZr)8L16]·2(Cp4Zr2(µ-O)Cl2) (complex 1) (Cp = cyclopentadienyl anion; L = 4-fluorobenzeneseleninic acid) was prepared by the reaction of bis(cyclopentadienyl)zirconium dichloride with 4-fluorobenzeneseleninic acid and characterized by elemental analysis, infrared spectroscopy, 1H, 13C NMR spectroscopy, ESI-MS, XRD and X-ray diffraction. The structure analysis shows that complex 1 is a centrosymmetric 32-membered macrocycle containing an eight-nuclear zirconocene. In this complex, the 4-fluorobenzeneseleninic acid ligands adopt bidentate mode in coordinating to zirconium, which play a bridging role in the formation of a macrocycle. The title compound is a rare example of aromatic selenic acid-based zirconocene derivatives. Furthermore, the preliminary in vitro anti-tumor activity of complex 1 has also been studied toward breast cancer cell lines (MDA-MB-231) and human cervix cell lines (HeLa). The results indicate that complex 1 shows higher activity compared with the ligand and bis(cyclopentadienyl)zirconium dichloride.