The preparation and characterisation of rhodium(III) and Iridium(III) half sandwich complexes with napthalene-1,8-dithiolate, acenaphthene-5,6-dithiolate and biphenyl-2,2′-dithiolate

The synthesis of rhodium(III) and iridium (III) half sandwich complexes [Cp*M(PEt3) (S-R-S)], M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (NaphthS2, a), acenaphthene-5,6-dithiolate (AcenapS2, b) and biphenyl-2,2′-dithiolate (BiphenS2, c) is reported. We also describe the isolation of a new compound acenaphthene-1,8-dithiol. All complexes have been fully characterised using multinuclear NMR spectroscopy and single crystal X-ray diffraction. The ligands naphthalene-1,8-dithiol (H2a), acenaphthene-1,8-dithiol (H2b), 1,1′-biphenyl-2,2′-dithiol (H2c) and benzene-1,2-dithiol (H2d) have also been characterised by single crystal X-ray diffraction.PostprintPeer reviewe

Main group tellurium heterocycles anchored by a P2VN2 scaffold and their sulfur/selenium analogues

The authors are grateful to the EPSRC, the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea, the School of Chemistry St. Andrews, EaStCHEM, and NSERC Canada for financial support.A comprehensive investigation of reactions of alkali-metal derivatives of the ditelluro dianion [TePV(NtBu)(μ-NtBu)]22– (L2–, E = Te) with p-block element halides produced a series of novel heterocycles incorporating P2VN2 rings, tellurium, and group 13–16 elements. The dianion engages in Te,Te′-chelation to the metal center in Ph2Ge and R2Sn (R = tBu, nBu, Ph) derivatives; similar behavior was noted for group 14 derivatives of L2– (E = S, Se). In the case of group 13 trihalides MCl3 (M = Ga, In), neutral spirocyclic complexes (L)M[NtBu(Te)PV(μ-NtBu)2PIIIN(H)tBu)] (M = Ga, In) comprised of a Te,Te′-chelated ligand L2– and a N,Te-bonded ligand resulting from loss of Te and monoprotonation were obtained. In reactions with RPCl2 (R = tBu, Ad, iPr2N) a significant difference was observed between Se- and S-containing systems. In the former case, Se,Se′-chelated derivatives were formed in high yields, whereas the N,S-chelated isomers predominated for sulfur. All complexes were characterized by multinuclear (1H, 31P, 77Se, 119Sn, and 125Te) NMR spectroscopy; this technique was especially useful in the analysis of the mixture of (L)(Se) and (L)(SeSe) obtained from the reaction of Se2Cl2 with L2– (E = Te). Single-crystal X-ray structures were obtained for the spirocyclic In complex (9), (L)GePh2 (E = Te, 10), (L)SntBu2 (E = Te, 12a); E = Se, 12aSe, E = S, 12aS) and (L)(μ-SeSe) (E = Te, 16).PostprintPostprintPeer reviewe

Synthesis and structural characterization of Zn2+, Cd2+ and Hg2+ complexes with tripyrrolidinophosphine chalcogenides

Authors are grateful to the Tunisian Ministry of High Education and Scientific Research for support [grant number: LR99ES14] and to the French Service for Cooperation and Cultural Action (SCAC) in Nouakchott, Mauritania for a scholarship to KE.Six new complexes of zinc(II), cadmium(II) and mercury(II) chlorides with tripyrrolidinophosphine chalcogenides of the types [MCl2(Pyrr3PE)2] (M = Zn, E = S (1) or E = Se (2); M = Cd, E = S (3) or E = Se (4)) and [{HgCl(Pyrr3PE)}2(µ-Cl)2] (E = S (5) or Se (6)) have been prepared in yields of 66-92% by reaction of the ligands with metal chloride in ethanol and characterized by 1H and 31P NMR, IR, elemental analysis, conductivity, and single crystal X-ray diffraction analysis. The results show that the complexes are pseudo-tetrahedral containing coordinated chloride ions. Interestingly, the X-ray studies reveal that while the title ligands produce dinuclear complexes with Hg, their Cd and Zn complexes are mononuclear. The tetrahedral bond angles vary from 85.69(5)° to 126.25(4)° in dinuclear complexes 5 and 6 and from 93.51(3)° to 117.38(3)° in mononuclear species 2-4. The E = S bond lengths are in the range 1.999(9)-2.198(2) Å. The coordination properties of the title ligands are discussed and compared to those obtained for their bulkier counterparts.PostprintPeer reviewe

The Synthesis of [{n-Bu2Sn(S2N2)}2] and its use in the preparation of Organometallic Iridium Sulfur Nitrogen Complexes

The addition of [n-Bu2SnCl2] to a solution of [S4N3][Cl] in liquid ammonia gave after extraction of the dry reaction mixture the new tin disulfur dinitrido compound [{n-Bu2Sn(S2N2)}(2)] (1). Reaction of [{n-Bu2Sn(S2N2)}(2)] (1) with the pentamethylcyclopentadienyl (Cp*) iridium derivatives [{IrCl(mu-Cl)(eta(5)-C5Me5)}(2)] or [(eta(5)-C5Me5)IrCl2(PPh3)] gave different products, which were dependent on the reactant ratios. A 1:1 reaction between 1 and [{IrCl(mu-Cl)(eta(5)-C5Me5)}(2)] gave only [(eta(5)-C5Me5)Ir(S2N2)] (2) in moderate yield; the same product in higher yield was obtained from a 2:1 reaction between 1 and [(eta(5)-C5Me5)IrCl2(PPh3)]. Reaction of 1 and [(eta(5)-C5Me5)(2)IrCl2(PPh3)] (1:1 molar ratio) in the presence of NH4[PF6] gave the unusual bimetallic species [(eta(5)-C5Me5)IrCl(PPh3)(S2N2)Ir(eta(5)-C5Me5)][PF6] (3). The X-ray crystal structures of 1, 2, and 3 are reported.PostprintPeer reviewe

THE PREPARATION OF METALLA-SULPHUR/SELENIUM COMPLEXES FROM REACTIONS IN LIQUID AMMONIA

The preparation of metalla-sulphur-nitrogen and metalla-selenium-nitrogen complexes from reactions in liquid ammonia is described. For example, reaction of PtCl2(PR3)2 with [S4N3]Cl in liquid ammonia yields Pt(S2N2)(PR3)2. Similar reactions with SOCl2 SO2Cl2 and SeCl4 give complexes containing NSO-, [SO2(NH)2]2- and Se2N22- ligands respectively

[Disulfanediylbis(ferrocenylthiophosphinato)-? 2O,O] titanocene tetra-hydro-furan tris-olvate

The title compound, [Fe 2Ti(C 5H 5) 4)(C 10H 8O 2P 2S 4)]·3C 4H 8O, contains a central seven-membered TiO 2P 2S 2 ring with a very similar geometry compared to the derivative showing anisyl instead of ferrocenyl substituents, the Ti-O distance being marginally longer for the anisyl derivative. Two tetra-hydro-furan solvent mol-ecules are each disordered on a twofold axis

A novel polyoxo(thio)molybdenum(V) sulfite compound: Synthesis and crystal structure of {Mo-2(V)(mu-S)(2)O-2](6)(mu(3)-SO3)(4)(mu-SO3)(12)}(20-)anion

The non-cyclic polyoxo(thio) molybdate(V)-sulfite K-6(NH4)(14){Mo-2(V)(mu-S)(2)O-2](6)(mu(3)-SO3)(4)(mu-SO3)(12)} . 7H(2)O 1 was prepared by self-condensation of Mo-2(V)(mu-S)(2)O-2](2+) building block in the presence of (NH4)(2)SO3. Compound 1 was characterized by X-ray structure analysis as well as IR, UV-vis spectroscopies and thermogravimetric analysis

Polyoxovanadium(IV) sulfite compounds: Synthesis, structural, and physical studies

An unexplored family of polyoxometalates has evolved through the synthesis and structural characterization of vanadium(IV) sulfite heteropolyanions. The hexanuclear vanadium(IV) compound, which is ferromagnetic down to 2 K, exhibits a unique structural motif for such metal species, with a central cubic {M<sub>4</sub>O<sub>2</sub>(OH)<sub>2</sub>} fragment and metal centers at two of the corners of the cluster

Coordination of an amino alcoholic Schiff base ligand toward the zinc(II) ion:spectral, structural, theoretical, and docking studies

Funding: This study was supported by the Iran National Science Foundation (INSF).A new zinc(II) complex of 2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol (L), [Zn(Lz)Br2] ( 1 ), is prepared and identified by elemental analysis, FTIR and 1H NMR spectroscopy, and single crystal X-ray diffraction. The X-ray structure analysis of 1 reveals a tetrahedrally coordinated zinc(II) complex containing the NO-donor amino alcoholic Schiff base ligand and two bromo ligands. After complexation, the ligand (L) converts to its zwitterionc form (Lz) of phenol → phenolate; amine → ammonium. In this structure, hydrogen bonds between amine and alcohol units form different types of hydrogen bond motifs, including R12(7),R22(7), R22(10), R44(24), R44(30), R66(38), and R66(44). In addition to the hydrogen bonds in this crystal network, there are π–π stacking interactions between the phenyl ring and the imine group. The ability of the ligand and its isostructural complexes [Zn(Lz)Br2] ( 1 ), [Zn(Lz)Cl2] ( 2 ), and [Zn(Lz)I2] ( 3 ) to interact with ten selected biomacromolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II, and B-DNA) is investigated by docking studies. The results show that in some cases, the studied compound can interact with proteins and DNA better than doxorubicin. The charge distribution pattern of the ligand and complex 1 is studied by the NBO analysis.PostprintPeer reviewe

Synthetic, structural, and spectroscopic studies of sterically crowded tin-chalcogen acenaphthenes

A series of sterically encumbered peri-substituted acenaphthenes have been prepared containing chalcogen and tin moieties at the close 5,6-positions (Acenap[SnPh3][ER], Acenap = acenaphthene-5,6-diyl, ER = SPh (1), SePh (2), TePh (3), SEt (4); Acenap[SnPh2Cl][EPh], E = S (5), Se (6); Acenap[SnBu2Cl][ER], ER = SPh(7), SePh (8), SEt (9)). Two geminally bis(peri-substituted) derivatives ({Acenap[SPh2]}2SnX2, X = Cl (10), Ph (11)) have also been prepared, along with the bromo–sulfur derivative Acenap(Br)(SEt) (15). All 11 chalcogen–tin compounds align a Sn–CPh/Sn–Cl bond along the mean acenaphthene plane and position a chalcogen lone pair in close proximity to the electropositive tin center, promoting the formation of a weakly attractive intramolecular donor–acceptor E···Sn–CPh/E···Sn–Cl 3c-4e type interaction. The extent of E→Sn bonding was investigated by X-ray crystallography and solution-state NMR and was found to be more prevalent in triorganotin chlorides 5–9 in comparison with triphenyltin derivatives 1–4. The increased Lewis acidity of the tin center resulting from coordination of a highly electronegative chlorine atom was found to greatly enhance the lp(E)−σ*(Sn–Y) donor–acceptor 3c-4e type interaction, with substantially shorter E–Sn peri distances observed in the solid state for triorganotin chlorides 5–9 (∼75% ∑rvdW) and significant 1J(119Sn,77Se) spin–spin coupling constants (SSCCs) observed for 6 (163 Hz) and 8 (143 Hz) in comparison to that for the triphenyltin derivative 2 (68 Hz). Similar observations were observed for geminally bis(peri-substituted) derivatives 10 and 11.</p