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Reaction of various sulphur ligands L (SEt−, SPh−, SC6F4H-4−, SEt2, StBu2, SnBu2, DMSO, DPSO) with the precursors [(COD)M(R)Cl] (COD = 1,5-cyclooctadiene, M = Pd or Pt; R = methyl (Me) or benzyl (Bn); DMSO = dimethyl sulfoxide; DPSO = diphenyl sulfoxide) allowed isolation and characterisation of mononuclear neutral (n = 0) or cationic (n = 1) complexes [(COD)Pt(R)(L)]n+. Reaction of l -cysteine (HCys) with [(COD)Pt(Me)Cl] under similar conditions gave the binuclear cationic complex in [{(COD)Pt(Me)}2(μ-Cys)]Cl. Detailed NMR spectroscopy and single crystal X-ray diffraction in the case of [(COD)Pt(Me)(SEt2)][SbF6] and [(COD)Pt(Me)(DMSO)][SbF6] reveal markedly labilised Pt–S bonds as a consequence of the highly covalent Pt–C bonds of the R coligands in these organometallic species. Cationic charge (n = 1) seems to lower the Pt–S bond strength further. Consequently, most of these complexes are not stable long-term in aqueous DMF (N,N-dimethylformamide) solutions. This made the evaluation of their antiproliferative properties towards HT-29 colon carcinoma and MCF-7 breast adenocarcinoma cell lines impossible. Only the two complexes [(COD)Pt(R)(SC6F4H-4)] with R = Me or SC6F4H-4 coligands could be tested with the R = Me complex showing promising activity (in the range of cisplatin), while the R = SC6F4H-4 derivative is largely inactive, as were the phosphane complexes [(dppe)Pt(SC6F4H-4)2] (dppe = 1,2-bis(diphenylphosphino)ethane), cis-[(PPh3)2Pt(SC6F4H-4)2] and cis-[(PPh3)2PtCl2] which were tested for comparison. In turn, our findings might pave the way to new Pt anti-cancer drugs with largely reduced unwanted depletion of incorporated drugs and reduced side-effects from binding to S-containing biomolecules.

The synthesis, spectroscopy, structures and chemical reactivity of platinum(II) diolefin complexes cis-[(∥∧∥)PtCl2], cis-[(∥∧∥)PtCl(R)] and cis-[(∥∧∥)Pt(R)2] [∥∧∥ = chelate diolefin ligand: 1,5-cyclooctadiene (COD), 1,5-dimethylocta-1,5-diene (Me2COD), norbornadiene (NBD), 1,5-hexadiene (HEX), 3-allyloxypropene (All2O, diallyl ether), diallylamine (All2NH); R = Me, Bn, C6F5, C6F4H-4 (or -5), or C≡C(4-Me)Ph] have been explored. The relative exchange rates of the cis-[(∥∧∥)PtCl2] complexes towards the diimine ligand diisopropyl-1,4-diazabutadiene (iPr-DAB) increased along the series COD < Me2COD < NBD < HEX < All2O by a factor of 4. The presumably dimeric complex [(All2NH)PtCl2]2 undergoes a unique rearrangement process in dimethyl sulfoxide (DMSO) solution to yield the dimeric piperazine complex [PtCl(dmso)(C6H10N)]2, which has been characterised by single-crystal XRD. For selected platinum complexes, cytotoxic effects in HT-29 colon carcinoma and MCF-7 breast cancer cell lines were evaluated. For comparison, the dicationic complexes [(COD)Pt(Bn)(L)][PF6]2 with the very labile coligands N-methyl-4,4′-bipyridinium (MQ+) and N-methyl-1,4-pyrazinium (Mpz+) were added to the study. Although the hexadiene complexes [(HEX)Pt(C6F4H-4)2] and [(HEX)Pt(C6F4H-5)2] show strong cytotoxicity, the introduction of labile diolefin ligands or the labile cationic MQ+ or Mpz+ coligands does not generally lead to markedly increased cytotoxicity.

The reaction of HSC6F4H-4 and base with suitable platinum(II) chlorido precursor complexes leads to mononuclear complexes containing diimine ligands [(N^N)Pt(SC6F4H-4)2], or [(N^N)Pt(Me)(SC6F4H-4)] (N^N = 2,2′-bipyridine (bpy), dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or 11-trifluoromethyl-dipyrido[3,2-a:2′,3′-c]phenazine (CF3dppz)), cycloocta-1,5-diene (COD) complexes [(COD)Pt(SC6F4H-4)2] or [(COD)Pt(R)(SC6F4H-4)] (R = Me, Bn (benzyl) or C6F5), or phosphine complexes cis-[(PPh3)2Pt(SC6F4H-4)2], [(dppe)Pt(SC6F4H-4)2] (dppe = 1,2-bis(diphenylphosphino)ethane) and [(dppb)Pt(C6F5)(SC6F4H-4)] (dppb = 1,4-bis(diphenylphosphino)butane). Reaction of cis-[(DMSO)2PtCl2] lead to the labile cis- and trans-[(DMSO)2Pt(SC6F4H-4)2] which rapidly lose DMSO to yield polymeric [Pt(SC6F4H-4)2]m. Reaction of HSC6F4H-4 and KOtBu with K2PtCl4 gave K2[Pt(SC6F4H-4)4]. The new compounds were analysed and characterised by single crystal XRD, 1H, 19F and 195Pt NMR and IR spectroscopy. Both single crystal XRD (in the solid) and NMR (in solution) reveal that the ligand strength of the thiolate ligand −SC6F4H-4 strongly depends on the further ligands in the complexes. The crystal structures exhibit various inter- and intra molecular π stacking interactions of the SC6F4H-4 coligands. The absorption spectroscopy and electrochemistry of the diimine complexes [(N^N)Pt(SC6F4H-4)2] (N^N = bpy, dppz and CF3dppz) have been investigated and reveal that the Pt complexes are superior to the recently reported Pd derivatives in view of their application in photoactive materials.

The reaction of HSC6F4H-4 or KSC6F4H-4 with the palladium(II) complexes [(NN)PdCl2] [NN = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen)] leads to the mononuclear palladium complexes [(NN)Pd(SC6F4H-4)2] or [(NN)PdCl(SC6F4H-4)], whereas the reaction with [(COD)PdCl2] (COD = 1,5-cyclooctadiene) results in the loss of COD and the formation of the oligonuclear species [Pd(SC6F4H-4)2]m. For NN = phen, the compound [(phen)2K(μ-phen)2K(phen)2][(4-HC6F4S)2Pd(μ-SC6F4H-4)2Pd(SC6F4H-4)2] containing a homoleptic dimeric dianionic Pd complex was also obtained. The reaction of KSC6F4H-4 with PdCl2 yielded K2[Pd(SC6F4H-4)4]. The new compounds were analysed and characterised by single-crystal XRD, 1H and 19F NMR spectroscopy and IR spectroscopy. The UV/Vis absorption spectroscopy and electrochemistry of [(bpy)Pd(SC6F4H-4)2] have been investigated and are compared to those of the related Pt derivative [(bpy)Pt(SC6F5)2].

A reaction of YI3, dibenzo-24-crown-8 and iodine in ethanol yielded, as a by-product, red single crystals of (I2)@(db24c8). In the triclinic crystal, P-1, a = 485.0(1), b = 1203.7(3), c = 1280.4(2) pm, α = 64.56(2)°, β = 86.82(2)°, γ = 83.89(2)°, V = 671.1(2) × 106.pm3, Z = 1, R1= 0.0301 for 1965 reflections with I0 > 2σ(I0), iodine molecules with an I–I distance of 268.39(7) pm, slightly longer than in the gas phase, are included in a matrix of db24c8 molecules.

The crystal structure of Hg(C6F4-o-NO2)21 is planar with intramolecular Hg–O coordination whereas those of the polymorphs of Hg(C6F4-m-NO2)22a and 2b have the two aryl rings rotated relative to each other (87° and 59°). At a supramolecular level, both complexes exhibit weak Hg⋯O interactions. Theoretical calculations (B3LYP and MP2) for gas-phase Hg(C6F4-o-NO2)2 and Hg(C6F4-m-NO2)2 molecules predict non-planar conformations in both complexes corresponding to one polymorph of the latter (2a). However, when the supramolecular Hg⋯O interactions are included, using a dimeric model, the calculations more accurately predict the observed structures of 1 and 2b.

The mononuclear complex, [Co(TAMEN)](ClO(4))(2) (DMSO), containing the Mannich base N,N'-tetra-(4-antipyrylmethyl)-1,2-diaminoethane (TAMEN) as ligand, was synthesized and characterised by conductometric, electronic and infrared spectroscopic properties. The single-crystal X-ray structure show the presence of two well defined units, [Co(TAMEN)](2+) and (ClO(4))(-). The complex cation contains cobalt(II) in the pseudo octahedral environment created by the N(2)O(4) donor set of TAMEN. The cobalt(II) complex have been screened for its cytotoxic activity against three cultured human cell lines established from hepatoma (Hep G2), breast (MCF-7) and lung (A549) cancers as well as on non-tumor bovine kidney (MDBK) cells. The cytotoxic activity of the ligand TAMEN was assessed on one tumor (Hep G2) and one non-tumor (MDBK) cell lines. The cobalt(II) compound was found to decrease in a time- and concentration- dependent manner the viability of tumor (A549, MCF-7, Hep G2) cell lines, while the ligand TAMEN expressed proliferative activity on hepatoma (HepG2) and bovine kidney (MDBK) cells, especially after prolonged incubation.

The two lead(II) coordination polymers [Pb(4,4′-dm-2,2′-bpy)(Dca)(NO3)]n (1) and [Pb(4,4′-dmo-2,2′-bpy)(Dca)(NO3)]n (2) were prepared by treatment of lead(II) nitrate, sodium dicyanamide with 4,4′-dimethyl-2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine, respectively. Both polymers were characterized by elemental analysis, IR and 1H NMR spectroscopy, thermogravimetric analysis and X-ray crystallography. The coordination polymers can be described as one-dimensional double-chains with Pb(II) centers bridged by Dca and nitrate co-ligands, containing trinuclear rings, [Pb3(L)3(NO3)2(Dca)], and bridging nitrate and Dca co-ligands in cis and trans positions, respectively. The coordination number of the Pb(II) ions in 1 and 2 is seven, with the PbN4O3 coordination polyhedron containing a stereochemically active lone pair of electrons with hemi-directed coordination spheres. The polymer chains form networks via supramolecular interactions that include O⋯O, C H⋯O, C H⋯N interactions, in addition to hydrogen bonding and π–π stacking.

Three new 1:1 complexes of lead(II) with the pincer-type ligand 4′-chloro-2,2′:6′,2″-terpyridine (TpyCl), [Pb(TpyCl)(NO3)2]n (1), [Pb(TpyCl)(ClO4)2]n (2) and [Pb(TpyCl)Br2]2 (3), have been synthesized and characterized by X-ray crystal structure determination as well as spectroscopy and thermal analysis. 1 and 2 are coordination polymers in which the coordination polyhedra are linked via nitrate and perchlorate ligands, respectively, to chains. 3 exhibits a dimeric molecular structure with Pb(μ-Br)2Pb type bridging. In all three compounds the chains and the oligomers are connected to networks via supramolecular interactions which include O···O, C–H···O, C–H···Cl and C–H···Br hydrogen bonding and π–π stacking as well.

The 1:1 (arene)mercury complexes [HgR2(arene)] [R = C6F4-o-NO2, C6F4-m-NO2, C6F4-o-H, C6F5; arene = TMB (1,2,4,5-tetramethylbenzene), PMB (1,2,3,4,5-pentamethylbenzene)] are readily formed when mixtures of the mercurial and arene are crystallised from CH2Cl2 or CH2Cl2/hexane. Analogous 1:1 complexes are also formed from Hg(C6F5)(2) and PhMe, whereas novel 1:2 complexes [HgR2(arene)(2)] result from Hg(C6F4-o-NO2)(2) and PhMe or TMO (1,2,4-trimethoxybenzene) and from Hg(C6F5)(2) and TMO. In the crystalline state, the 1:1 [HgR2(arene)] complexes exist as canted columns of alternating planar HgR2 and arene layers linked by weak (Hg center dot center dot center dot C 3.2-3.5 angstrom) eta(1) or eta(2) pi-arene-mercury interactions. For the TMB (R = C6F4-o-NO2, C6F4-o-H, C6F5) and PhMe (R = C6F5) complexes, the packing of neighbouring columns shows aligned, alternating fluoroarene and arene ring planes resulting in a 2D brick-wall motif with potential supramolecular components (fluoroarene-fluoroarene and fluoroarene-arene stacking). For the TMB complex with R = C6F4-m-NO2 the 2D array is distorted into a herringbone motif by weak C-H center dot center dot center dot O interactions. The 1:2 complex [Hg(C6F4-o-NO2)(2)-(PhMe)(2)] has an analogous mercury environment to the 1:1 complexes, and the packing shows a distinct layer structure of alternating rows of PhMe and HgR2 with two PhMe units per HgR2 unit but with no inter-stack interactions. The TMO complexes have long Hg center dot center dot center dot O contacts (3.2 angstrom.) rather than Hg center dot center dot center dot C and similarly show a layered structure, but in this case, with a single column of alternating HgR2 and pairs of TMO. Theoretical calculations for the 1:2 [HgR2(TMB)(2)] Complexes (R = C6F4-o-NO2, C6F4-m-NO2) are consistent with the findings from the observed crystal structures.

Molecular Complexes and Coordination Polymers of Divalent Mercury with the 4-N-Ligand 6,7-Dimethyl-2,3-di-(2′-pyridyl)-chinoxaline (Dpc) Single crystals of six 6,7-dimethyl-2,3-di-(2′-pyridyl)-chinoxaline (Dpc) complexes of divalent mercury with –CF3, -SCN, -NO3, -I, -Br, and -Cl as the ligands have been obtained mostly by slow evaporation of solutions of the mercuric salts Hg(CF3)2, Hg(SCN)2, Hg(NO3)2, HgI2, HgBr2, or HgCl2 and Dpc. The crystal structures were determined by single crystal X-ray diffraction: [Hg(CF3)2(Dpc)] (1) [monoclinic, P21/c (no. 14), a = 815.7(1), b = 2780.2(4), c = 1036.5(1) pm, β = 99.78(1)°, V = 2316.5(4) 106 pm3, Z = 4, R1 [I0 > 2σ(I0)] = 0.0334], [Hg(SCN)2(Dpc)] (2) [triclinic, (no. 2), a = 817.4(2), b = 1075.8(2), c = 1427.0(3) pm, α = 110.48(2), β = 103.02(3), γ = 94.42(3)°, V = 1128.5(4) 106 pm3, Z = 2, R1 [I0 > 2σ(I0)] = 0.0425], [(HgCl2)2(Dpc)](CH3CN) (3) [triclinic, (no. 2), a = 942.8(1), b = 950.6(1), c = 1486.9(2) pm, α = 80.18(1), β = 79.57(1), γ = 87.73(1)°, V = 1291.3(3) 106 pm3, Z = 2, R1 [I0 > 2σ(I0)] = 0.0469], [HgBr2(Dpc)] (4) [monoclinic, C2/c (no. 15), a = 792.9(1), b = 2411.5(5), c = 1261.5(2) pm, β = 102.11(2)°, V = 2358.5(6) 106 pm3, Z = 4, R1 [I0 > 2σ(I0)] = 0.0354], [HgI2(Dpc)] (5), [monoclinic, C2/c (no. 15), a = 4162.2(17), b = 747.8(2), c = 1509.4(5) pm, β = 111.16(3)°, V = 4369.0(20) 106 pm3, Z = 8, R1 [I0>2σ(I0)] = 0.0547], [Hg(NO3)2(Dpc)](H2O) (6) [monoclinic, P21/c (no. 14), a = 1256.1(2), b = 1257.8(2), c = 1482.1(3) pm, β = 116.44(1)°, V = 2096.6(6) 106 pm3, Z = 4, R1 [I0 > 2σ(I0)] = 0.0414]. The crystal structures of 2, 3 and 5 consist of molecular complexes, those of 1, 4 und 6 exhibit coordination polymers. In all cases, HgII has a characteristic coordination number of, essentially, CN = 2, to different ligator atoms, C in 1, S in 2, Cl, Br, and I in 3-5 as well as N in 6.

In the monohydrate Pr(OOC-Ph-NH2)3(H2O) (1), Pr3+ is nine-coordinate with only oxygen atoms coordinating. Two carboxylate groups are bidentate-bridging, four are tridentate-bridging and there is one coordinating water molecule, hence the coordination number is nine. The chains run along [0 1 0]. In the anhydrous Pr(OOC-Ph-NH2)(OOC-Ph-NH) (2), the central Pr3+ ion is surrounded by six oxygen atoms and two nitrogen atoms in a distorted square antiprism. These polyhedra are connected to each other via two opposite O–O edges to form chains running parallel [0 0 1]. The chains, in which all carboxylate groups are tridentate-bridging, are arranged in a centered rectangular fashion and are further connected via OOC-Ph-NH bridging.

Complexes of Monovalent Dibenzo-18-crown-6 Cations with Triiodide as Anions The new polyiodides [NH4(db18c6)]2(I3)2 (1), [NH4(db18c6)](db18c6)I3 (2), [Na1/2(db18c6)H2O]2I3 (3), [Rb(db18c6)]I3 (4), [Rb(db18c6)]2(I3)2 (5), [Cs(db18c6)]I3 (6), and [Cs2(db18c6)3][Cs(db18c6)3/2](I3)3 (7) were obtained from reactions of dibenzo-18-crown-6 (db18c6) and iodine with NH4I, NaI, RbI, and CsI. Their crystal structures were determined by single-crystal X-ray diffraction. (1) M = NH4, (5) M = Rb: monoclinic, P21/n, a = 1409,67(8), b = 2211,63(14), c = 1627,16(10) pm, β = 101,030(5)°, Z = 4 (crystal data for M = NH4); (2): monoclinic, Pn, a = 1345,26(14), b = 773,82(4), c = 2095,10(20) pm, β = 94,439(8)°, Z = 2; (3): orthorhombic, Pnaa, a = 931,59(13), b = 2213,3(5), c = 2223,9(4) pm, Z = 4; (4): monoclinic, P21/n, a = 999,50(6), b = 1711,33(10), c = 1517,45(9) pm, β = 99,021(5)°, Z = 4; (6): triclinic, , a = 705,16(9), b = 1137,93(14), c = 1678,90(20) pm, α = 73,719(10), β = 79,782(10), γ = 83,669(10)°, Z = 2; (7): triclinic, , a = 1519,25(6), b = 1702,49(7), c = 2136,41(9) pm, α = 102,641(3), β = 101,989(3), γ = 91,911(3)°, Z = 2. 1 : 1 cations centered by M, [M(db18c6)]+, are found in the structures of (1 – 6). In contrast, the triple decker cation found in (7) is less common. The crystal structures are completed by mostly asymmetrically linear I3− anions.

Five new compounds in the system (NH4)Cl/HgCl2/H2O have been obtained as colourless single crystals, (NH4)Hg5Cl11, (NH4)2Hg3Cl8(H2O), (NH4)4Hg3Cl10(H2O)2, (NH4)2HgCl4(H2O), and (NH4)10Hg3Cl16. In all of these, as in HgCl2 itself, (almost) linear HgCl2 molecules persist with Hg-Cl distances varying from 229 to 236 pm. In (NH4)10Hg3Cl16 there are also tetrahedra [HgCl4] with d(Hg-Cl) = 247 pm present. If larger Hg-Cl distances (of up to 340 pm) are considered as belonging to the coordination sphere of HgII, the structures may be described as consisting of isolated octahedra and tetrahedra as in (NH4)10Hg3Cl16, edge-connected chains as in (NH4)2HgCl4(H2O), edge-connected chains and layers of octahedra as in (NH4)4Hg3Cl10(H2O)2, corrugated layers of edge-connected octahedra as in (NH4)2Hg3Cl8(H2O), and, finally, a three-dimensional network of connected six- and seven-coordinate Hg-Cl polyhedra as in (NH4)Hg5Cl11. The water molecules are never attached to HgII. The (NH4)+ cations, and sometimes Cl− anions, play a role for electroneutrality only.

Rare-Earth-Metal Coordination Polymers: Syntheses and Crystal Structures of Six New Pimelinates, [M(Pim)(PimH)(H2O)](H2O) (M = Ce, Pr) and [M2(Pim)3(H2O)4] (M = Tb, Ho, Er, Tm) The new rare-earth metal carboxylates [M(Pim)(PimH)(H2O)](H2O) (M = Ce (1), Pr (2)) and [M2(Pim)3(H2O)4] (M = Tb (3), Ho (4), Er (5), Tm (6)) were prepared from the reaction of pimelinic acid with CeO2, Pr6O11, Tb4O7, HoCl3, ErCl3 and Tm(NO3)3, respectively. Their crystal structures were determined by single-crystal X-ray diffraction. [M(Pim)(PimH)(H2O)](H2O) crystallize in the monoclinic space group P21/n (no. 14) with a = 909.6(1), b = 870.6(1), c = 2240.5(2) pm, β = 92.30(1)°, Z = 4 (crystal data for M = Ce). The isostructural pimelinate-hydrates [M2(Pim)3(H2O)4] crystallize with orthorhombic symmetry, Pbcn (no. 60), with a = 1392.5(1), b = 902.3(1), c = 2408.8(2) pm, Z = 4 (crystal data for M = Tb). The rare-earth cations have coordination numbers of 10 (1, 2) and 9 (3, 4, 5 and 6), respectively. In the crystal structure of [M(Pim)(PimH)(H2O)](H2O) bidentate and tridentate-bridging carboxylate groups form rather dense structures in which chains are bridged to layers and further to networks. Pimelinic acid molecules fill the channels. In [M2(Pim)3(H2O)4] tridentate-bridging carboxylate groups coordinating to two rare-earth ions lead to dimers that are linked with other dimers to strands. The channels thus formed between the strands are rather small in diameter. They do not contain any non-coordinated water molecules.

New Polyiodides of Cesium containing Double and Triple Decker Cations, [Cs(benzo-18-crown-6)2]Ix and [Cs2(benzo-18-crown-6)3](Ix)2 (x = 3, 5) [Cs(b18c6)2]Ix (x = 3 (1), 5 (3)) and [Cs2(b18c6)3](Ix)2 (x = 3 (2), 5 (4)) (b18c6 = benzo-18-crown-6) have been synthesized by the reaction of benzo-18-crown-6 (C16H24O6), cesium iodide (CsI) and iodine (I2) in acetonitrile (1), ethanol/dichloromethane (2, 4) and 2-methoxyethanol (3). Their crystal structures were determined on the basis of single crystal X-ray data {(1): monoclinic, C2/c, Z = 4, a = 2048.8(5), b = 1329.5(5), c = 1588.7(5) pm, β = 110.23(1)°; (2): monoclinic, C2/c, Z = 4, a = 2296.0(1), b = 2092.7(1), c = 1373.6(1) pm, β = 100.21(1)°; (3): monoclinic, P21/n, Z = 4, a = 1586.3(1), b = 1745.5(1), c = 1608.6(1) pm, β = 92.37(1)°; (4): triclinic, , Z = 2, a = 1241.7(1), b = 1539.8(2), c = 1938.4(2) pm, α = 91.15(1), β = 100.53(1), γ = 95.26(1)°}. As expected, double decker cations centered by Cs atoms, [Cs(b18c6)2]+, are found in the structures of (1) and (3). In contrast, the triple decker cation found in (2) and (4) is less common. The triiodide anions of (1) and (2) can be regarded as normal and the chain-type pentaiodide anions of (3) and (4) fall into the known systematic sequence of these anions. The differences in the connectivity of the crystallographically independent I5− anions in (4) are surprising with respect to the fact that, so far, independent pentaiodide anions do not show variations in their scheme of connectivity within one crystal structure.

The series of cis / trans -trifluoromethylselenato complexes [Pt(SeCF 3 ) 2 − x Cl x (PPh 3 ) 2 ] ( x = 0, 1) was identified by NMR spectroscopic methods. While in acetonitrile solution spectra are dominated by the resonances of the cis derivatives, those of pure cis -[Pt(SeCF 3 ) 2 (PPh 3 ) 2 ] indicate cis – trans -isomerisation in CH 2 Cl 2 solution. In contrast, exchange reactions of cis -[PtCl 2 (PPh 3 ) 2 ] and [NMe 4 ]TeCF 3 only gave evidence for cis isomers. Molecular structures of cis - and trans -[Pt(SeCF 3 ) 2 (PPh 3 ) 2 ] and cis -[Pt(TeCF 3 ) 2 (PPh 3 ) 2 ] are discussed in comparison with related compounds.

[{Hg(CF3)2}(ThpH)(H2O)](H2O) (1), [{Hg4(Thp)4}(ClO4)4(H2O)8](H2O)4 (2), [{Hg(ThpH)2} (NO3)](NO3) (3) and {Hg(Thp)Cl}(H2O) (4) (ThpH = theophylline, C7H8N4O2) have been synthesized by slow evaporation of aqueous solutions of the mercuric salts Hg(CF3)2, Hg(ClO4)2, Hg(NO3)2, or HgCl2 and theophylline. Their crystal structures were determined on the basis of single crystal X-ray data. The coordination polymers 1 and 2 crystallize with triclinic symmetry, P1̅ (no. 2), with a = 468.8(2), b = 1256.4(5), c = 1445.5(6) pm, α = 67.15(3), β = 89.21(3), γ = 89.40(3)° and a = 833.6(1), b = 1862.7(2), c = 2182.9(2) pm, α = 111.61(1), β = 90.98(1), γ = 95.51(1)°, respectively. 3 and 4 crystallize with monoclinic symmetry, Pc (no. 7), a =1194.1(1), b=1258.8(2), c=735.5(2) pm, β =96.96(2)° and P21/n (no. 14), a=1069.0(2), b =911.6(1), c=1089.9(2) pm and β = 96.87(2)°. In 1 the theophylline molecules are non-coordinating to mercury and leave the Hg(CF3)2 molecule unchanged. Only weak electrostatic attractions to one keto-oxygen atom of theophylline and one water molecule hold this co-crystallisate together. In 2, the theophyllinate anion, Thp−, strongly coordinates with both N(7) and N(9) to HgII forming a large ring with eight Hg atoms that incorporates the water molecules. One sort of nitrate ions in 3 is weakly attached to HgII with the theophylline molecules still bound strongly through N(9). The chloride ligand and the theophyllinate ion seem to have the same strengths as ligands in 4 as they are both attached to HgII with the shortest distances possible

Rare-Earth-Metal Coordination Polymers: Synthesis and Crystal Structures of Five New Adipinates, [M2(Adi)3(H2O)4](AdiH2)(H2O)4 (M = La, Nd), [Er(Adi)(H2O)5]Cl(H2O) and [M(Adi)(H2O)5](NO3)(H2O) (M = Gd, Er) The new rare-earth compounds [M2(Adi)3(H2O)4](AdiH2)(H2O)4 (M = La (1), Nd (2)), [Er(Adi)(H2O)5]Cl(H2O) (3) and [M(Adi)(H2O)5](NO3)(H2O) (M = Gd (4), Er (5)) were obtained from the reaction of adipinic acid with La(OH)3·xH2O, Nd2O3, ErCl3·6H2O, Gd(NO)3·xH2O and Er2O3, respectively. Their crystal structures were determined by single-crystal X-ray diffraction. The coordination polymers [M2(Adi)3(H2O)4](AdiH2)(H2O)4 crystallize in the triclinic space group (no. 2) with a = 875.4(1), b = 1000.4(2), c = 1179.0(2) pm, α = 74.70(1), β = 69.85(1), γ = 86.18(2)° and Z = 1 (crystal data for M = La, (1)). The quasi-isostructural compounds [Er(Adi)(H2O)5]Cl(H2O) (3) and [M(Adi)(H2O)5](NO3)(H2O) (M = Gd (4), Er (5)) crystallize with monoclinic symmetry, space group C2/c (no. 15) with lattice parameters of a = 1231.5(1), b = 1532.6(1), c = 895.4(1) pm, β = 123.44(1)° and Z = 4 (crystal data for (3)). The rare-earth cations have the coordination numbers 10 (1, 2) and 9 (3, 4 and 5), respectively. The compounds [M2(Adi)3(H2O)4](AdiH2)(H2O)4 are constructed of infinite chains of edge-sharig [MO8(H2O)2] polyhedra that are cross-linked by adipinic acid molecules to form framework structures. In [Er(Adi)(H2O)5]Cl(H2O) (3) and [M(Adi)(H2O)5](NO3)(H2O) (M = Gd (4), Er (5)) the central cations are bridged by adipinic acid molecules in a bidentate-chelating manner to positively charged zigzag chains. Between these the counter ions and crystal water molecules are incorporated.

Four stanna-closo-dodecaborate complexes of ruthenium have been prepared and characterized by multinuclear NMR studies in solution and in the solid state. The solid-state structures of the dimeric zwitterions [[Ru(dppb)(SnB11H11)]2] (2) (dppb = bis(diphenylphosphino)butane), [[Ru(PPh3)2(SnB11H11)]2] (3), and the dianionic ruthenium complex [Bu3MeN]2[Ru(dppb)[2,7,8-(mu-H)3-exo-SnB11H11](SnB11H11)] (4) were determined by X-ray crystal structure analysis; they establish an unprecedented structural motif in the chemistry of heteroboranes and transition-metal fragments with the stanna-closo-dodecaborate moiety as a two-faced ligand that exhibits eta1(Sn) as well as eta3(B-H) coordination. The eta3-coordinated stannaborate in 4 and in the isostructural compound [Bu3MeN]2[Ru(PPh3)2[2,7,8-(mu-H)3-exo-SnB11H11](SnB11H11)] (5) shows fluxional behavior, which was studied in detail by using 31P[1H] EXSY and DNMR experiments. The activation parameters for the dynamic process of 5 are given.

Ligand exchange reactions of cis-PtCl2(PPh3)2 and [NMe4]SCF3 in different ratios were studied. Depending on the stoichiometry reactions proceeded with formation of products expected for the chosen ratio, i. e. cis-Pt(SCF3)Cl(PPh3)2, cis-Pt(SCF3)2(PPh3)2, and [NMe4][Pt(SCF3)3(PPh3)]. Starting from cis-PtCl2(MeCN)2 and [NMe4]SCF3 and adding PPh3 after substitution, product mixtures were dominated by the corresponding trans-isomers. Results of the single crystal structure analyses of cis-Pt(SCF3)2(PPh3)2 and trans-Pt(SCF3)Cl(PPh3)2 are discussed.

4-Tetrafluoropyridyl silver(I), AgC5F4N, has been obtained from Me3SiC5F4N and AgF in nearly quantitative yield. Reactions with bis(triphenylphosphoranyliden)ammonium chloride, [PNP]Cl, gave crystalline material of the composition [PNP][Ag(C5F4N)2]. Redox transmetallations of AgC5F4N and group 12–14 elements Zn, Cd, Hg, Ga, In, Sn yielded the corresponding 4-tetrafluoropyridyl element compounds. The molecular structures of [PNP][Ag(C5F4N)2], Hg(C5F4N)2, Ga(C5F4N)3 · EtCN · H2O, In(C5F4N)3 · 2EtCN and Sn(C5F4N)4 are discussed.

Colourless single crystals of three piperazine (Pip) complexes of divalent mercury with -CF3 and SCN- as the ligands have been obtained from aqueous and ethanolic solution of the respective components Hg(CF3)2, Hg(SCN)2, and piperazine. The crystal structures were determined by single crystal X-ray diffraction: Hg(CF3)2(Pip) (1) [monoclinic, C2/c, Z = 4, a = 891.2(1), b = 1649.8(2), c = 777.7(1) pm, β = 101.27(2)°, R1(all) = 0.0413], Hg(SCN)2(Pip) (2) tetragonal, P42/ncm, Z = 4, a = 840.8(1), c = 1511.0(1) pm, R1(all) = 0.0479], (Hg(SCN)2)2(Pip) (3) [triclinic, , Z = 1, a = 590.6(1), b = 738.6(2), c = 919.5(2) pm, α = 88.96(2)°, β = 82.80(2)°, γ = 78.21(2)°, R1(all) = 0.0582]. In 1 and 2 zig-zag chains are observed with the piperazine molecule only weakly attached to the Hg(CF3)2 molecule. The Hg(SCN)2(Pip) chains in 2 condense to double chains in 3 where half of the piperazine molecules are missing. In both, 2 and 3, Hg2+ is coordinated in a distorted tetragonal fashion by two N and two S ligator atoms from piperazine and SCN- ligands, respectively.

Rare-Earth-Metal Coordination Polymers: Syntheses and Crystal Structures of Three New Glutarates, [Pr2(Glu)3(H2O)4] · 10.5H2O, [Pr(Glu)(H2O)2]Cl, and [Er(Glu)(GluH)(H2O)2] The new rare-earth dicarboxylates [Pr2(Glu)3(H2O)4] · 10.5H2O (1), [Pr(Glu)(H2O)2]Cl (2) and [Er(Glu)(GluH)(H2O)2] (3) were obtained from the reactions of glutaric acid with PrCl3·6H2O and Er(OH)3, respectively. The crystal structures were determined by single-crystal X-ray diffraction. [Pr2(Glu)3(H2O)4] · 10,5H2O crystallizes in the orthorhombic space group Pnma (no. 62) with a = 871.7(4), b = 3105.0(9), c = 1308.3(9) pm and Z = 4. The crystals of [Pr(Glu)(H2O)2]Cl are monoclinic (I2/a; no. 15) with a = 786.2(1), b = 1527.6(2) c = 801.2(1) pm, β = 99.78(1)° and Z = 4. [Er(Glu)(GluH)(H2O)2] crystallizes in the monoclinic space group P21/a (no. 14) with lattice parameters of a = 882.4(1), b = 1375.3(2), c = 1267.4(2) pm, β = 107.13(1)° and Z = 4. The rare-earth cations have the coordination numbers 10 (1), 8 + 1 (2) and 9 (3). The individual polyhedra are connected to chains and further to sheets in 1 and 2 and to double chains in 3. Only in the water-rich compound 1 there are channels that contain crystal water molecules. It, therefore, has a considerably lower density than 2 and 3.

Pr(Man)3(ManH) and Er(Man)3(H2O)2 (ManH = mandelic acid) have been synthesized by slow evaporation of aqueous solutions of rare-earth salts (Pr(OH)3, ErCl3 · 6H2O) with mandelic acid (α-hydroxy-phenyl acetic acid, C8H8O3) and their crystal structures were determined on the basis of X-ray data. In the crystal structure of Pr(Man)3(ManH) (1) (monoclinic, P21, a = 574.8(1), b = 3042.5(4), c = 908.4(1) pm, β = 92.09(2)°, Z = 2) the Pr(III) ions are surrounded by eight oxygen atoms in a distorted square antiprismatic fashion with distances Pr-O in the range 241 to 254 pm. These polyhedra are connected by coordinative bonds to chains paralleling the crystallographic [100] direction. In Er(Man)3(H2O)2 (2) (orthorhombic, P212121, a = 577.7(3), b = 1816.3(13), c = 2329.4(13) pm, Z = 4) the crystal structure contains isolated complexes with octa-coordinated erbium atoms chelated by three mandelate anions through one of their carboxylate oxygen atoms and the alcoholic hydroxyl group. Two water molecules complete the distorted square antiprismatic coordination sphere.

Pentaiodides of Complex Alkaline Metal Crown Ether Cations: Synthesis and Structural Characterisation of the Compounds [M(benzo-15-crown-5)2]I5, M = Na, K, Rb and Cs The isotypic compounds [M(benzo-15-crown-5)2]I5, M = Na, K, Rb and Cs are obtained as single crystals via the reaction of benzo-15-crown-5, MI and iodine (2 : 1 : 2) from ethanol/dichloromethane (1 : 1). These compounds crystallize in the monoclinic space group P21/n with four formula units in the unit cell. The cations form typical sandwich complexes. The volume of the unit cell increases by 4, 3 % from the sodium to the caesium compound, corresponding to the increasing space required by the cations. The pentaiodide units consist of a elongated triiodide unit and two iodine half-molecules. These iodine molecules are completed by centres of symmetry. The interconnection between the pentaiodide units leads to the formation of zig-zag chains that run along [001]. Considering the strongly different ionic radii of the alkali-metal cations, the existence of this number of isotypic structures is rather surprising.

Reaction of chloropropyl-substituted stanna-closo-dodecaborate [Cl(CH 2 ) 3 SnB 1 1 H 1 1 ] - with the nucleophile Li[CH 2 PPh 2 ] provided a straightforward synthesis of an anionic phosphane [Ph 2 PCH 2 SnB 1 1 H 1 1 ] - . Derivatization of the phosphane was carried out in reaction with sulfur and hydrochloric acid to give [Bu 3 MeN][Ph 2 P(S)CH 2 SnB 1 1 H 1 1 ] and the zwitterion [Ph 2 P(H)CH 2 SnB 1 1 H 1 1 ]. In reaction with various transition metal electrophiles, complexation reactions were accomplished resulting in the isolation of trans-substituted palladium and platinum complexes [Bu 3 MeN] 2 [trans-(Ph 2 PCH 2 SnB 1 1 H 1 1 ) 2 MCl 2 ] (M = Pd, Pt), a neutral silver adduct [(acetone)Ag(Ph 2 PCH 2 SnB 1 1 H 1 1 )], and a linearly coordinated bisphosphane of gold [Bu 3 MeN][Au(Ph 2 PCH 2 -SnB 1 1 H 1 1 ) 2 ]. The solid state structures of the ligand salt, the palladium and gold coordination compounds were determined and discussed.

From aqueous solutions containing acetylenedicarboxylic acid and Na2CO3 or KOH single crystals of Na2(C2(COO)2)(H2O)4 (P21/n, Z = 2) and K2(C2(COO)2)(H2O) (P1̅, Z = 2) were obtained by slow evaporation of the solvent. In Na2(C2(COO)2)(H2O)4 the sodium atom is co-ordinated almost octahedrally by three water molecules and three oxygen atoms of the carboxylate ligands. These octahedra are connected to layers, which are held together by hydrogen bonds. In K2(C2(COO)2)(H2O) two crystallographic distinct potassium ions exist both seven co-ordinate by oxygen atoms stemming from water molecules and carboxylate ligands. These KO7 polyhedra are linked to a threedimensional structure by the bifunctional carboxylate anions and the water molecules.

[(18-C-6)K]2[Hg(CF3)2SCN]2(1) und [P(CH3)(C6H5)3]2[Hg(CF3)2X]2 (X = Br (2), I (3)) werden synthetisiert und deren Kristallstrukturen bestimmt. [(18-C-6)K]2[Hg(CF3)2SCN]2(1) kristallisiert in der monoklinen Raumgruppe P21/c mit Z = 2, [P(CH3)(C6H5)3]2[Hg(CF3)2Br]2(2) in der monoklinen Raumgruppe P21/n mit Z = 2 und [P(CH3)(C6H5)3]2[Hg(CF3)2I]2(3) in der triklinen Raumgruppe P1¯ mit Z = 1. Alle drei Verbindungen bilden in den Festkorpern dimere uber Br, I bzw. SCN verbruckte Anionen mit planaren Hg2X2- Ringen. Die Strukturparameter der Hg(CF3)2-Gruppen in den bisher bekannten Bis(trifluormethyl)halogenomercuraten werden verglichen. Es liegt jeweils eine nahezu symmetrische und eine verzerrte CF3-Gruppe vor. Die groste Differenz in den C—F-Bindungslangen wird in [(18-C-6)K][Hg(CF3)2I] gefunden. Dies kann als experimenteller Beweis fur die Eigenschaft von Trifluormethylquecksilber-Verbindungen gedeutet werden, in Gegenwart von Alkalimetalliodiden als exzellente Difluorcarbenquelle zu wirken. Structures of Bis(trifluoromethyl)halogeno and thiocyanato Mercurates, [Hg(CF3)2X]— (X = Br, I, SCN), and a Comparison of the Structural Parameters of the CF3 Groups [(18-C-6)K]2[Hg(CF3)2SCN]2(1) and [P(CH3)(C6H5)3]2[Hg(CF3)2X]2 (X = Br (2), I (3)) are prepared and their crystal structures are determined. [(18-C-6)K]2[Hg(CF3)2SCN]2(1) crystallizes in the monoclinic space group P21/c with Z = 2, [P(CH3)(C6H5)3]2[Hg(CF3)2Br]2(2) in the monoclinic space group P21/n with Z = 2 and [P(CH3)(C6H5)3]2[Hg(CF3)2I]2(3) in the triclinic space group P1¯ with Z = 1. In the solid state the three compounds form dimeric anions with planar Hg2X2 rings. The structural parameters of the Hg(CF3)2 units in the till now known bis(trifluoromethyl)halogeno mercurates are compared. In all compounds one nearly symmetric and one distorted CF3 group exist. The largest differences of the C—F bond lengths is found for [(18-C-6)K][Hg(CF3)2I]. This can be regarded as the experimental evidence for the properties of trifluoromethyl mercury compounds to act as excellent difluorocarbene sources in the presence of alkali iodides.

The reactions of H2C[C(Me)N(C6H3-2, 6-i-Pr2)]2 ((DPP)2NacNacH) and Zn(C6F5)2 · 2 EtCN or Cd(C6F5)2 · 2 MeCN in a molar ratio of approximately 1:1 selectively gave the derivatives (DPP)2NacNacMC6F5 (M = Zn, Cd) in excellent yields. No reaction was observed between (DPP)2NacNacH and Hg(C6F5)2 under similar conditions. Reactions with Hg(C6F5)OCOMe yielded the products of dismutation, Hg(C6F5)2 and Hg(OCOMe)2. (DPP)2NacNacZnC6F5 crystallises as a 1:1 adduct with THF with two independent molecules per unit cell (triclinic, P1 (no. 2)). The zinc atom is tetrahedrally surrounded by the chelating ligand, the pentafluorophenyl group and one THF molecule. A similar situation is found in the 1:1 adduct of (DPP)2NacNacCdC6F5 and DMF (monoclinic, P21/n (no. 14)), while in the donor-free compound (CDCl3 and H2O co-crystallize) the cadmium atom is nearly ideally trigonal planar co-ordinated (orthorhombic, Pbnm (no. 62)). Synthesen, Charakterisierungen und Kristallstrukturen von s-Diketiminato-Verbindungen der Pentafluorphenylverbindungen der Elemente der Gruppe 12, HC{[C(Me)N(C6H3-2, 6-i-Pr2)]2}MC6F5 (M = Zn, Cd) Die Reaktionen von H2C[C(Me)N(C6H3-2, 6-i-Pr2)]2 ((DPP)2NacNacH) und Zn(C6F5)2 · 2 EtCN bzw. Cd(C6F5)2 · 2 MeCN in einem molaren Verhaltnis von ungefahr 1:1 fuhren selektiv zu den Verbindungen (DPP)2NacNacMC6F5 (M = Zn, Cd) in sehr guten Ausbeuten. Zwischen (DPP)2NacNacH und Hg(C6F5)2 werden unter ahnlichen Bedingungen keine Reaktionen beobachtet. Umsetzungen mit Hg(C6F5)OCOMe fuhren zu Dismutierungen in Hg(C6F5)2 und Hg(OCOMe)2. (DPP)2NacNacZnC6F5 kristallisiert als 1:1 Addukt mit THF mit zwei unabhangigen Molekulen je Elementarzelle (triklin, P1 (Nr. 2)). Das Zinkatom in dieser Verbindung ist tetraedrisch durch den Chelatliganden, die Pentafluorphenylgruppe und ein THF-Molekul koordiniert. Eine vergleichbare Koordination wird in dem Addukt aus (DPP)2NacNacCdC6F5 und DMF (monoklin, P21/n (Nr. 14)) gefunden, wohingegen in der Donator-freien Verbindung (CDCl3 und H2O kokristallisieren) das Cadmiumatom nahezu ideal trigonal planar koordiniert ist (orthorhombisch, Pbnm (Nr. 62)).

The thermally unstable compound [Hg[P(C(6)F(5))(2)](2)] was obtained from the reaction of mercury cyanide and bis(pentafluorophenyl)phosphane in DMF solution and characterized by multinuclear NMR spectroscopy. The thermally stable trinuclear compounds [Hg[(mu-P(CF(3))(2))W(CO)(5)](2)] and [Hg[(mu-P(C(6)F(5))(2))W(CO)(5)](2)] are isolated and completely characterized. The higher order NMR spectra exhibiting multinuclear satellite systems have been sufficiently analyzed. [Hg[(mu-P(CF(3))(2))W(CO)(5)](2)].2DMF crystallizes in the monoclinic space group C2/c with a = 2366.2(3) pm, b = 1046.9(1) pm, c = 104.0(1) pm, and beta = 104.01(1) degrees. Structural, NMR spectroscopic, and vibrational data prove a weak coordination of the two DMF molecules. Structural, vibrational, and NMR spectroscopic evidence is given for a successive weakening of the pi back-bonding effect of the W-P bond in the order [W(CO)(5)PH(R(f))(2)], [Hg[(mu-P(R(f))(2))W(CO)(5)](2)], and [W[P(R(f))(2)](CO)(5)](-) with R(f) = C(6)F(5) and CF(3). The pi back-bonding effect of the W-C bonds increases vice versa.

A series of zwitterionic molecules was synthesized by nucleophilc substitution between stanna-closo-dodecaborate and a series of alkyliodides like (ω-iodo-alkyl)trialkyl-ammoniumiodides and 1-(4-iodobutyl)pyridiniumiodide. The structures in the solid state have been determined by X-ray crystal structure analysis for Bu3N-C3H6-SnB11H11 (3), Pr3N-C4H8-SnB11H11 (6), Bu3N-C4H8-SnB11H11 (7) and C5H5N-C4H8-SnB11H11 (9). Zwitterionische Molekule mit Stanna-closo-dodecaborat Eine Reihe von zwitterionischen Molekulen wurden durch nukleophile Substitution zwischen dem Stanna-closo-dodecaborat Cluster sowie verschiedenen Iodalkyl-Verbindungen wie (ω-Iod-alkyl)-trialkyl-ammoniumiodiden und 1-(4-Iodbutyl)pyridiniumiodid dargestellt. Von den Derivaten Bu3N-C3H6-SnB11H11 (3), Pr3N-C4H8-SnB11H11 (6), Bu3N-C4H8-SnB11H11 (7) und C5H5N-C4H8-SnB11H11 (9) wurde die Struktur im Festkorper mittels Rontgenstrukturanalyse bestimmt.

A boron-bridged amido-cyclopentadienyl ligand was recently shown to form constrained-geometry titanium-complexes that are capable of olefin polymerisation. Here, the synthesis of the corresponding amido-indenyl ligand η1-C9H7B(NiPr2)N(H)Ph (C9H7=indenyl) (2a/2v) and its allyl–vinyl isomerisation are discussed. Deprotonated 2a reacts with ZrCl4 to give the strongly distorted zirconocene-type complex [Zr{η5:η1-C9H6B(NiPr2)NPh}2] (3) in a 2:1 reaction. All compounds have been characterised by multinuclear NMR methods and structures of both the ligand 2a and the complex 3 have been confirmed by X-ray diffraction.

[Bis(dimethylamino)ethanediylidene]bis(dimethylammonium) bis(trifluoromethylchalcogenates(0)), (TDAE)[ECF3]2 (E = Se, Te), are quantitatively formed from the reductions of E2(CF3)2 with tetrakis(dimethylamino)ethene, TDAE. Both compounds are bright yellow to orange solids which crystallize isostructurally with the corresponding sulfur derivative in the orthorhombic space group Pbca (No. 61). (TDAE)[SeCF3]2 has alternatively been prepared by cation exchange from [NMe4]SeCF3 and (TDAE)Br2. Trifluormethylselenat(0), [SeCF3]—, und Trifluormethyltellurat(0), [TeCF3]— — kristalline Produkte der Reduktion von Bis(trifluormethyl)dichalkogen Verbindungen, E2(CF3)2 (E = Se, Te), mit Tetrakis(dimethylamino)ethen (TDAE) [Bis(dimethylamino)ethandiyliden]bis(dimethylammonium)bis(trifluormethylchalcogenate(0)), (TDAE)[ECF3]2 (E = Se, Te), werden quantitativ durch Reduktion von E2(CF3)2 mit Tetrakis(dimethylamino)ethen, TDAE, gebildet. Beide Verbindungen sind leuchtend gelbe bzw. orange Materialien, die isostrukturell mit dem entsprechenden Schwefelderivat in der orthorhombischen Raumgruppe Pbca (Nr. 61) kristallisieren. (TDAE)[SeCF3]2 wurde alternativ durch Kationenaustausch aus [NMe4]SeCF3 und (TDAE)Br2 synthetisiert.

The stabilization of the P(CF3)2- ion by intermediary coordination to the very weak Lewis acid acetone gives access to single crystals of [18-crown-6-K]P(CF3)2. The X-ray single crystal analysis exhibits nearly isolated P(CF3)2- ions with an unusually short P−C distance of 184(1) pm, which can be explained by negative hyperconjugation and is also found by quantum chemical hybrid DFT calculation. Coordination of the P(CF3)2- ion to pentacarbonyl tungsten has only a minor effect on electronic and geometric properties of the P(CF3)2 moiety, while a strong increase in thermal stability of the dissolved species is achieved. The hitherto unknown P(C6F5)2- ion is stabilized by coordination to pentacarbonyl tungsten and isolated as a stable 18-crown-6 potassium salt, [18-crown-6-K][W{P(C6F5)2}(CO)5], which is fully characterized. The tungstate, [W{P(C6F5)2}(CO)5]-, decomposes slowly in solution, while coordination of the phosphorus atom to a second pentacarbonyl tungsten moiety results in an enhanced thermal stab...

Bis((Z)-5-phenyl-2-phenylmethylidene-1, 3-dithiole-4-yl)monosulfane (6), a molecule consisting of two diphenyldithiafulvene units connected by a sulfur bridge, was synthesized by the selective lithiation of (Z)-4-phenyl-2-phenylmethylidene-1, 3-dithiole (7a) at the endocyclic double bond and by subsequent reaction of the lithiated intermediate with bis(phenylsulfonyl)sulfane. Since this reaction sequence proceeded with retention of configuration, of three possible isomers (E, E, Z, E, and Z, Z) only the Z, Z form was obtained. On the basis of the X-ray structure analysis and the NMR-spectroscopic characterization of 6 supplemented by the NMR parameters of (E)- and (Z)-4-phenyl-2-phenylmethylidene-1, 3-dithiole, it was demonstrated that two characteristic 5J coupling constants of the proton at the exocyclic double bond indicate the configuration (Z or E) of disubstituted dithiafuvene derivatives. Ein neues Monomer fur π-konjugierte Polymere — Synthese und Charakterisierung von Bis((Z)-5-phenyl-2-phenylmethyliden-1, 3-dithiol-4-yl)monosulfan Bis((Z)-5-phenyl-2-phenylmethyliden-1, 3-dithiol-4-yl)monosulfan (6), ein Molekul, das aus zwei uber eine Schwefelbrucke verbundenen Diphenyldithiafulven-Einheiten besteht, wurde durch selektive Lithiierung von (Z)-4-phenyl-2-phenylmethyliden-1, 3-dithiol (7a) an der endocyclischen Doppelbindung und nachfolgende Umsetzung des lithiierten Intermediats mit Bis(phenylsulfonyl)sulfan dargestellt. Da die Reaktionsfolge unter Erhaltung der Konfiguration ablauft, wurde von drei moglichen Isomeren (E, E, Z, E, und Z, Z) nur die Z, Z-Form erhalten. Auf der Grundlage der Rontgenstrukturanalyse und der NMR-spektroskopischen Charakterisierung von 6, erganzt durch die NMR-Parameter von (Z)- and (E)-4-Phenyl-2-phenylmethyliden-1, 3-dithiol, wurde gezeigt, das zwei charakteristische 5J Kopplungskonstanten des Protons an der exocyclischen Doppelbindung die Konfiguration (E oder Z) disubstituierter Dithiafulvenderivate anzeigen.

Bei den Umsetzungen von Hg(Rf)2 (Rf = CF3, C6F5) mit [(18-C-6)K]X (X = Br, I) in CH2Cl2 oder H2O bilden sich die Mercurate [(18-C-6)K][Hg(Rf)2X] in guten Ausbeuten. Die Trifluormethylverbindungen [(18-C-6)K][Hg(CF3)2X] kristallisieren isotyp in der monoklinen Raumgruppe P21; die azentrische Raumgruppe wird durch Messung des optischen SHG-Effektes bestatigt. [(18-C-6)K][Hg(C6F5)2Br] kristallisiert in der monoklinen Raumgruppe P21/n und [(18-C-6)K][Hg(C6F5)2I] in der triklinen Raumgruppe P1¯. In allen vier Kristallen liegen die Anionen monomer mit T-formiger Umgebung des Quecksilbers vor. Die Massenspektren sowie die thermische Stabilitat der Mercurate werden beschrieben. Syntheses and Structures of Perfluoroorganohalogeno Mercurates [Hg(Rf)2X]— (Rf = CF3, C6F5; X = Br, I) [(18-C-6)K][Hg(Rf)2X] (Rf = CF3, C6F5; X = Br, I) are prepared from the reactions of Hg(Rf)2 with [(18-C-6)K]X in CH2Cl2 or H2O in good yields. The trifluoromethyl compounds [(18-C-6)K][Hg(CF3)2X] crystallize isotypically in the monoclinic space group P21; the acentric space group is proved by measurements of the optical SHG effect. [(18-C-6)K][Hg(C6F5)2Br] crystallizes in the monoclinic space group P21/n and [(18-C-6)K][Hg(C6F5)2I] in the triclinic space group P1¯. The anions of the crystalline compounds are monomeric with a T-shaped surrounding of the Hg atoms. Mass spectra and the thermal stability of the mercurates are described.

The reactions of [SnB11H11]2− with organic halides like 1-chloro-3-iodopropane, allylbromide, propargylbromide and 2,6-bis-(bromomethyl)pyridine lead in a nucleophilic substitution at room temperature to the products [Bu3MeN][Cl(CH2)3SnB11H11] (4), [Bu3MeN][H2CCHCH2SnB11H11] (6), [Bu4N][HCCCH2SnB11H11] (7), and [Bu4N]2[2,6-(H11B11SnCH2)2(C5H3N)] (8). In water Na2[SnB11H11] reacts with 2-bromoethylamine hydrobromide at 50 °C and 3-bromopropylamine hydrobromide at 70 °C to the zwitterionic products [H11B11Sn(CH2)nNH3] (n=2, 3), which were characterized by X-ray crystal structure analysis. [H11B11Sn(CH2)2NH3] crystallizes with one equivalent of water under the formation of NHO hydrogen bonding. In the case of chloroiodomethane and diiodomethane the substitution reaction proceeds differently and the monosubstituted components were not detected. The disubstituted compound [Bu3MeN]2[H2C(SnB11H11)2] (5), whose structure could be confirmed by X-ray crystal structure analysis, is the only observed reaction product.

The bis(trifluoromethyl)phosphanide ion, P(CF(3))(2)(-), decomposes slowly above -30 degrees C in CH(2)Cl(2) and THF solution. An increase of the thermal stability of the P(CF(3))(2)(-) moiety is observed if excess CS(2) is added. The P(CF(3))(2)(-) moiety is stabilized because of the formation of the bis(trifluoromethyl)phosphanodithioformate anion. Solutions of a [P(CF(3))(2)CS(2)](-) salt still act as a source of P(CF(3))(2)(-), even in the presence of excess of CS(2). The stable compound [18-crown-6-K][P(CF(3))(2)CS(2)] was characterized by multinuclear NMR spectroscopy, elemental analysis, and vibrational spectroscopy in combination with quantum chemical calculations. The thermally unstable P(C(6)F(5))(2)(-) ion decomposes even at -78 degrees C in solution giving polymeric material. The intermediate formation of the bis(pentafluorophenyl)phosphanide anion in the presence of excess of CS(2) allows the isolation of [18-crown-6-K][P(C(6)F(5))(2)CS(2)]. The novel compound crystallizes with one solvent molecule CH(2)Cl(2) in the monoclinic space group P2(1)/n with a = 1151.8(1) pm, b = 1498.1(2) pm, c = 2018.2(2) pm, beta = 102.58(1) degrees, and Z = 4. Optimized geometric parameters of the [P(C(6)F(5))(2)CS(2)](-) ion at the B3PW91/6-311G(d) level of theory are in excellent agreement with the experimental values.

[Ba(benzo-15-crown-5)2](I3)2 and [Ba(benzo-15-crown-5)2](I7)2 can be obtained in crystalline form by reacting benzo-15-crown-5 (C14H20O5), barium iodide (BaI2), and iodine (I2) in ethan-ole /dichloromethane. The triiodide consists of a sandwich-like cation [Ba(benzo-15-crown-5)2]2+ and an isolated symmetrically linear I3- anion. The unusual I7- anion in the heptaiodide can be described as a V-shaped pentaiodide unit, which is connected with a slightly widened iodine molecule to the rare Z-form of the heptaiodide ion. In the crystal structure, secondary bonding distances lead to almost planar ten-membered iodine rings, which are connected by common edges to form staircase-like bands.

[NMe(4)][R(f)Te(SC(S)NR(2))(2)] derivatives are selectively formed by the oxidation of [NMe(4)]TeR(f) (R(f) = CF(3), C(2)F(5)) with [R(2)NC(S)S](2) (NR(2) = NEt(2), NBz(2), N(CH(2))(4)) in almost quantitative yields. An alternative route to obtain the dithiocarbamato complex anions offer reactions of Te[SC(S)NR(2)](2) (NR(2) = NEt(2), NBz(2)) with equimolar amounts of Me(3)SiR(f) and [NMe(4)]F. Some of the derivatives were recrystallized with bulky cations in order to determine the crystal structures. Structural elucidation by diffraction methods exhibit the structural feature of a distorted pentagonal planar environment (resembling "butterflies") around the tellurium centres. The carbamato tellurates can be transferred easily into the neutral derivatives, R(f)TeSC(S)NR(2), upon treatment with Ag[BF(4)]. In solution they equilibrate with Te(2)(R(f))(2) and [R(2)NC(S)S](2) and finally are transformed into Te(R(f))(2), Te[SC(S)NR(2)](2), and Te[SC(S)NR(2)](4), respectively. All compounds are fully characterized by NMR spectroscopic methods ((1)H, (13)C, (19)F, (125)Te). Additionally, synthesis and characterization of the hitherto unknown derivative [NMe(4)]TeC(2)F(5) are described.

Lewis acid/Lewis base adduct formation of the P(CF 3 ) 2 - ion and acetone leads to a reduced negative hyperconjugation and, therefore, limits the C-F bond activation. The resulting increased thermal stability of the P(CF 3 ) 2 - ion in the presence of acetone allows selective substitutions and enables the synthesis of the first example of a chiral, bidentate bis(trifluoromethyl)phosphane ligand: a DIOP derivative, [(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)]bis(diphenyl-phosphane), in which the phenyl groups at the phosphorus atoms are replaced by strong electron-withdrawing trifluoromethyl groups. The resulting high electron-acceptor strength of the synthesized bidentate (CF 3 ) 2 P ligand is demonstrated by a structural and vibrational study of the corresponding tetracarbonyl-molybdenum complex. The stabilization of the P(CF 3 ) 2 - ion in the presence of acetone is based on the formation of a dynamic Lewis acid/Lewis base couple, (CF 3 ) 2 PC(CH 3 ) 2 O - . Although there is no spectroscopic evidence for the formation of the formulated alcoholate ion, the intermediate formation of (CF 3 ) 2 PC(CH 3 ) 2 O - could be proved through the reaction with (CF 2 ) 2 PP(CF 2 ) 2 , which yields the novel phosphane-phosphinite ligand (CF 3 ) 2 PC(CH 3 ) 2 OP(CF3)2. This ligand readily forms square-planar Pt(II) complexes upon treatment with solid PtCl 2 .

Chiral, bidentate phosphane ligands, so-called PP ligands, are most frequently synthesized by reacting chiral ditosylates with diarylphosphanide ions. To use the P(CF3)2− ion in nucleophilic substitution reactions, it is necessary to reduce the negative hyperconjugation, which is associated with a C–F activation. For this reason we synthesized different bis(trifluoromethyl)phosphanido complexes of mercury, silver and tungsten and investigated their use in nucleophilic substitution reactions. The most reactive compound, resulting from this study so far, is the pentacarbonylbis(trifluoromethyl)phosphanidotungstenate, [W{P(CF3)2}(CO)5]−, which exhibits nearly the same bonding situation for the P(CF3)2 unit as in the free P(CF3)2− ion. For use in synthesis of bis(trifluoromethyl)phosphane derivatives, Lewis acids are desirable, which stabilize the P(CF3)2− ion by an intermediary formation of a donor acceptor adduct and can be split off after the synthesis of bis(trifluoromethyl)phosphane derivatives, as could be achieved using the extremely weak Lewis acids, CS2 and acetone. These results could be established in the synthesis of the first example of an chiral, bidentate bis(trifluoromethyl)phosphane derivative. To synthesize a chiral, bidentate bis(pentafluorophenyl)phosphane derivative, a different synthetic strategy is necessary that does not involve the P(C6F5)2− ion, which decomposes even at low temperature. The implementation of functional P(CN)2− ions leads to the synthesis of functional, chiral bidentate dicyanophosphane derivatives which finally can be transformed into the corresponding bis(pentafluorophenyl)phosphane derivatives.

By reaction of KC(2)H and K(2)Zn(CN)(4) in liquid ammonia, the diammoniate K(2)Zn(C(2)H)(4).2NH(3) was obtained. K(2)Cd(C(2)H)(4).2NH(3) was synthesized by reacting KC(2)H, Cd(NH(2))(2), and acetylene in liquid ammonia. The crystal structures of the air and temperature sensitive compounds were determined by X-ray single crystal diffraction at low temperatures (T = 170 K). Both compounds crystallize in the monoclinic space group I2/a (No. 15) with Z = 4. K(2)Zn(C(2)H)(4).2NH(3): a = 7.289(1) A, b = 12.765(2) A, c = 14.066(2) A, beta = 98.11(2) degrees. K(2)Cd(C(2)H)(4).2NH(3): a = 7.444(1) A, b = 12.619(3) A, c = 14.304(2) A, beta = 98.94(1) degrees. Characteristic structural motifs are tetrahedral [M(C(2)H)(4)](2-) fragments (M = Zn, Cd) and zigzag chains of edge sharing distorted (C(2)H)(6) octahedra centered by potassium ions. These zigzag chains are connected by a second type of crystallographically distinct potassium ions that also bind to two ammonia molecules.

In the title compound, catena-poly[[[triaquacopper(II)]- micro -acetylenedicarboxylato-kappa(2)O:O"] hydrate], [[Cu(C(4)O(4))(H(2)O)(3)].H(2)O](n), the Cu(II) ion is coordinated by two monodentate carboxylate groups in trans positions and three water molecules, thus forming a fivefold coordination polyhedron that can be described as a distorted square pyramid. All atoms are located on general sites. The polyhedra are connected by bifunctional acetylenedicarboxylate ligands, to form almost linear chains parallel to [001]. Hydrogen bonds involving the non-coordinated water molecule connect these chains to form a three-dimensional framework.

In catena-poly[[[triaquacadmium(II)]-micro-acetylenedicarboxylato-kappa(4)O,O':O",O"'] hydrate], [[Cd(C(4)O(4))(H(2)O)(3)].H(2)O](n), the Cd(II) atom is coordinated by two bidentate carboxylate groups and three water molecules, thus forming a sevenfold coordination polyhedron with all atoms located on general sites. These polyhedra are connected by the bifunctional acetylenedicarboxylate ligands, forming zigzag chains running parallel to [120]. Hydrogen bonds, which involve the non-coordinated water molecule, connect these chains to form a three-dimensional framework.

The thermally unstable compounds Hg(CN)P(CF(3))(2) and Hg[P(CF(3))(2)](2) were obtained by reactions of mercury cyanide and bis(trifluoromethyl)phosphane in solution and characterized by multinuclear NMR spectroscopy. An increase in thermal stability is observed when the products form 18 valence electron complexes. The compounds [Hg(P(CF(3))(2))(2)(dppe)] (dppe = 1,2-bis(diphenylphosphanyl)ethane) and [Hg(P(CF(3))(2))(2)(Me(3)P)(2)] have been isolated in almost quantitative yield by reacting [Hg(CN)(2)(dppe)] or [Hg(CN)(2)(Me(3)P)(2)] with HP(CF(3))(2). [Hg(P(CF(3))(2))(2)(dppe)] crystallizes in the triclinic space group P1. The mercury atom is coordinated in a distorted tetrahedral fashion. The Hg-P(CF(3))(2) bonds, ca. 250 pm, are significantly longer than those of the mercury bis(phosphanides) Hg(PR(2))(2) with R = t-Bu, 245 pm, or SiMe(3), 241 pm. These easily accessible compounds [Hg(P(CF(3))(2))(2)(dppe)] and [Hg(P(CF(3))(2))(2)(Me(3)P)(2)] act as nucleophilic bis(trifluoromethyl)phosphane group transfer reagents.

The hydrolysis of [Hg{P(CF3)2}2(PMe3)2] yields colourless crystals of [Hg{OP(O)CF3(OH)}2(PMe3)3]. The proposed multistep reaction proceeds via primary hydrolysis of the starting material giving HgO and HP(CF3)2. The latter is directly oxidized by HgO to (CF3)2P(O)OH. The bis(trifluoromethyl)phosphinic acid hydrolyses to CF3P(O)(OH)2 which reacts with [Hg{P(CF3)2}2(PMe3)2] in the presence of PMe3 to the title compound. The crystal structure was determined by X-ray single-crystal analysis (triclinic; P1¯; a = 860.7(1), b = 1007.6(2), c = 1625.0(3) pm; α = 96.09(2), β = 101.09(2), γ = 107.79(2)°; Z = 2) and exhibits distorted trigonal bipyramidal mercury complexes which are connected to polymeric chains. The acidic units, {OP(O)CF3(OH)}—, are connected via intermolecular hydrogen bridges, forming two individual centrosymmetric eight membered rings with asymmetric hydrogen bridges with O—O distances of 249.4(8) and 250.8(8) pm. Synthese und Struktur von [Hg{OP(O)CF3(OH)}2(PMe3)3], ein verzerrt trigonal-bipyramidaler Komplex, der uber Wasserstoff-Brucken zu polymeren Ketten verknupft ist Bei der Hydrolyse von [Hg{P(CF3)2}2(PMe3)2] werden farblose Kristalle der Verbindung [Hg{OP(O)CF3(OH)}2(PMe3)3] erhalten. Der vorgeschlagene Reaktionsmechanismus der Hydrolyse verlauft uber die intermediare Bildung von HgO and HP(CF3)2. Letzteres wird durch HgO zu (CF3)2P(O)OH oxidiert. Die entstehende Bis(trifluormethyl)phosphinsaure hydrolysiert zu CF3P(O)(OH)2, welches in der Gegenwart von PMe3 mit [Hg{P(CF3)2}2(PMe3)2] zur Titelverbindung reagiert. Die Einkristall-Struktur-Analyse (triklin; P1¯; a = 860.7(1), b = 1007.6(2), c = 1625.0(3) pm; α = 96.09(2), β = 101.09(2), γ = 107.79(2)°; Z = 2) beschreibt verzerrt trigonal-bipyramidale Quecksilber-Komplexe, die zu polymeren Ketten verknupft sind. Die sauren Einheiten {OP(O)CF3(OH)}— sind uber intermolekulare, asymmetrische Wasserstoff-Brucken mit O—O Abstanden von 249.4(8) und 250.8(8) pm verknupft, die mit der Bildung von zwei individuellen, zentrosymmetrischen, achtgliedrigen Ringen einhergeht.

Te(C6F5)4 was prepared from the reactions of TeCl4 or Te(C6F5)2Cl2 with Grignard reagents or AgC6F5 in moderate to good yields. Substitution reactions with Me3SiX (X = Cl, Br, OSO2CF3), with equimolar amounts of Br2, with AgNO3 and with H[BF4] or BF3·OEt2 yielded the Te(C6F5)3X derivatives (X = Cl, Br, OSO2CF3, NO3, BF4). Oxidation reactions of Cd, Hg, and Pd0 complexes led to Te(C6F5)2 and the corresponding bis(pentafluorophenyl) derivatives M(C6F5)2 (M = Cd, Hg, Pd) and with InBr to In(C6F5)2Br. From very slow hydrolysis of Te(C6F5)4 the oxide Te(C6F5)2O was prepared. The thermal decomposition, the NMR and mass spectra of the partially new compounds are discussed. The crystal structures of Te(C6F5)3Br (monoclinic, P21/a, Z = 4), [Te(C6F5)3][OSO2CF3] (monoclinic, P21/n, Z = 16) and [Te(C6F5)2O]2 (triclinic, P1¯, Z = 2) were determined. Die Synthesen und Eigenschaften von Tetrakis(pentafluorphenyl)tellur, Te(C6F5)4, und verwandten Verbindungen — Rontgenstrukturanalysen von Tris(pentafluorphenyl)-tellurbromid, Te(C6F5)3Br, Tris(pentafluorphenyl)tellurtrifluormethansulfonat, [Te(C6F5)3][OSO2CF3] und Bis(pentafluorphenyl)telluroxid, Te(C6F5)2O Te(C6F5)4 wurde durch die Umsetzungen von TeCl4 bzw. Te(C6F5)2Cl2 mit Grignardreagenzien oder AgC6F5 in masigen bis guten Ausbeuten dargestellt. Durch Substitutionsreaktionen mit Me3SiX (X = Cl, Br, OSO2CF3), mit aquimolaren Mengen Br2, mit AgNO3 sowie mit H[BF4] bzw. BF3·OEt2 entstanden die Te(C6F5)3X-Verbindungen (X = Cl, Br, OSO2CF3, NO3, BF4). Oxidationsreaktionen von Cd-, Hg- und Pd0-Komplexen ergaben Te(C6F5)2 und die entsprechenden Derivate M(C6F5)2 (M = Cd, Hg, Pd); InBr wurde zu In(C6F5)2Br oxidiert. Durch sehr langsame Hydrolyse von Te(C6F5)4 wurde Te(C6F5)2O dargestellt. Die thermischen Zersetzungen sowie die NMR- und Massenspektren der teilweise neuen Verbindungen werden diskutiert. Die Kristallstrukturen von Te(C6F5)3Br (monoklin, P21/a, Z = 4), [Te(C6F5)3][OSO2CF3] (monoklin, P21/n, Z = 16) und [Te(C6F5)2O]2 (triklin, P1¯, Z = 2) wurden bestimmt.