Yuanda Chang

Electrochemical synthesis and crystal structure of silver(I) complexes with some heterocyclic thiones

Two silver(I) complexes, [{Ag(SR)}6][R1SH = 6-(tert-butyldimethylsilyl)pyridine-2-thione 1, R2SH = 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thione 2], have been synthesized by electrochemical oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones. The reaction of equimolar amounts of dppm [bis(diphenylphosphino)methane] with complexes 1 and 2 in dichloromethane resulted in the formation of [Ag4Cl4(dppm)2]3 and the elimination of RSCH2SR. Single-crystal X-ray analyses were performed for compounds 1, 3 and R2SCH2SR2.

Investigations into the syntheses and structures of clusters of the MoOREO32− systems (E = P and As)

The chemistry of the MoOREO32− sysems (E = P, As is remarkably diverse, exhibiting influences of the Mo oxidation state, solvent, organic substituents and reaction conditions of temperature, pressure and stoichiometry. Clusters exhibiting molybdenum nuclearities of two, four, five and six are common, as are species derived through both ligation to the Mo site and ligand-based transformations. Thus, the reactions of the Mo(VI) starting material [MoO2(acac)2] with the appropriate (REO3H2) or R′(PO3H2)2 provided a series of Mo(VI) clusters, with cyclic structures based on edge- and corner-sharing of Mo-octahedra and ligand tetrahedra. In contrast, when MoCl5 is used in the syntheses, a variety of reduced and mixed valence clusters are observed and metal-mediated ligand transformations are also common. Crystal data: (Et3NH)4[Mo4O10(C6H5PO3)4] · 2CH3CN (1): PI, a = 11.975(2), b = 12.442(2), c = 13.265(3), A, a = 81.87(3), β = 75.24(3), γ = 65.91(3)0, V = 1743.2(9)A3, Z = 1, R = 0.054 for 3577 independent reflections (I0 ≥ 3σ(I0)). Et3NH4)[Mo4O10 (C6H5AsO3)4] · 4H2O (2): P21ln, a = 11.243(2), b = 22.582(5), c = 14.665(3)A, β = 108.87(2)0, V = 3523(2)A3, Z = 2, R = 0.042 for 3412 reflections I0 ≥ 3σ(I0)). (Et3NH)4[Mo4O10{O3PCH2PO3}2] · 2CH3CH (3): P2121 a= 14.58(3), b = 17.084(3), c = 12.226(2)A, V = 3046(2)A3, Z = 2, R = 0.058 for 2000 reflections (I0 ≥ 3σ(I0)). (Et3NH)2[Mo4O10(CH3C6H4AsO3)2 (CH3C6H4AsO3H2] · H2) -(Et3NH)-(CH3C6H4AsO3H) (4): PI, a = 12.815(3), b = 13.668(3), c = 22.486(4)A, a = 92.76(2), β = 93.17(2), γ = 104.62(2)c, V = 3797(2)A, Z = 2, R = 0.051 for 5790 reflections (I0 ≥ 3σ(I0)). (Et3NH)2[Mo2O5{(C6H5)24] · CH3CN (5): PI, a = 11.102(2), b = 13.359(3), c = 22.000(4)A, α = 85.75(2), β = 89.29(2), γ = 89.6(2)0, V = 3254(2), V = 3254(2)A3, Z = 2, R = 0.061 for 6572 reflections I0 ≥ 3σ(I0)). (R3NH)4[Mo5O15(R′PO3)2] (R = CH2CH2CH3, R′ = −CH3) (6a): C2/c, a = 16.784(3)b = 17.855(4), c = 20.468(4)A, β = 96.49(2)0, Z = 4, R = 0.038 for 2854 reflections (I0 ≥ 3σ(I0)). (R′ = −CH2CH3, R′ = CH2C6H5 (6b): C2/c, a = 12.915(3), b = 19.860(4), c = 21.865(4)A, β = 102.38(2)0, V = 5433(3)A3, Z = 4, R = 0.076 for reflections I0 ≥ 3σ(I0)). (Et3NH)4[Mo6O18-(Bu1PO3)2] · Me2CO C2/c, a = 19.982(4), b = 13.481(3), c = 22.995(5)A, β = 112.70(2)0, V = 5716(3)A[su3, Z = 4, R = 0.075 for 2835 reflections (I0 ≥ 3σ(I0)). (Et3NH)4 [Mo6O18(H2NC6H4AsO3)2 (8): P21/c, a = 11.243(2), b = 11.355(2), c = 22.011(4)A, β = 99.87(1)0, V = 2764(1)A3, Z = 2, R = 0.040 for 2198 reflections (I0 ≥ 3σ(I0). (Mo2(OH)2Cl4{MeC6H4CH2, R = 0.070 for 2478 reflections (I0 ≥ 3σ(I0)). [Mo4O8(C6H5AsO2Cl)4Cl] · [MoOCl4] · 8H2) (10) P4/nnc, a = 11.385(2), c = 37.926(8)A, V = 4916(2)A3, Z = 4, R = 0.056 for 981 reflections (I0 ≥ 3σ(I0). [Mo4O8(CH3C6H4AsO2 Cl4Cl] · 8CH3OH · 9H2O (11): PI, a = 10.509(2), b = 12.154(2), c = 12.461(2)A, a = 88.09(2), β = 89.52(2), γ = 87.07(3)0, V = 1588.6(8)A3, Z = 2, R = 0.057 for 2618 reflections (I0 ≥ 3σ(I0)).

Electrochemical synthesis of mercury(II) complexes with some heterocyclic thiones: The crystal and molecular structures of bis(6-Tertbutyldimethylsilyl)2-Pyridyl disulphide (6-ButSidmepyS-Spy-6-BuSidme) and Hg(6-ButSidmepyS)2

Abstract A series of complexes of the type Hg(SR) 2 have been obtained by oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones (RSH). The crystal and molecular structures of bis(6-tertbutyldimethylsilyl)2-pyridyI disulphide (6-Bu t SidmepyS-Spy-6-Bu t Sidme) and of bis[(6-tertbutyldimethylsilyl) pyridyl-2-thionato] mercury(II), (Hg(6-Bu t SidmepyS( 2 ) have been determined by single crystal X-ray diffraction. The structure the mercury complex consists of individual centrosymmetric monomeric molecules with linear two coordination, SHgS and weak intramolecular HgN interactions. Vibrational and 1 H, 13 C and 199 Hg NMR spectral data of the complexes are discussed and related to the structure.

The reaction of copper 3-trimethylsilylpyridine-2-thiolate with bis(diphenylphosphino)ethane. Crystal structure of μ-[1,2-bis(diphenylphosphino)ethane]bis(3-trimethylsilylpyridine2-thiolato-S) [1,2-bis(diphenylphosphino)ethane]dicopper(I), [Cu2(3-Me3Sipyt)2(dppe)3]

μ-[1,2-Bis(diphenylphosphino)ethane]bis(3-trimethylsilyl;-pyridine-2-thiolate-S) [1,2-bis(diphenylphosphino)ethane] dicopper(I), [Cu2(3-Me3Sipyt)2(dppe)3], was obtained by reaction of [Cu(3-Me3Sipyt)] with 1,2-bis(diphenylphosphino) ethane (dppe) in acetone. The compound is dimeric with dppe molecules acting as both bridging and chelating ligands and the thione coordinating in the monoanionic form through the sulfur atom. The environment around the copper is distorted tetrahedral. Crystal data: P21n, a =16.640(3), b=14.437(3), c=18.321(4) A, β=101.41(3)°, V=4312(1) A3, Z=2, Dcalc=1.299 g cm−3, R=0.0627 for 2723 reflections.

Electrochemical synthesis and crystal structure of bis(4-methyl-6-trifluoromethylpyrimidine-2-thionate) cadmium(II)

Abstract Electrochemical oxidation of cadmium in a solution of 4-methyl-6-trifluoromethylpyrimidine-2-thione (MeCF 3 -pymtH) in acetonitrile gave [Cd(MeCF 3 -pymt) 2 ], whose crystal structure has been determined by X-ray diffraction. The structure of the compound consists of polymeric chains containing octahedrally cis coordinated cadmium atoms (CdN 2 S 4 ), with each ligand acting in an N,S-bidentate sulfur-bridging mode. Vibrational, 1 H and 13 C spectra of the complex are discussed and related to the structure.

Synthesis and structural characterization of complexes of the {Cp*Rh} and MeRe cores with pyridine-2-thiol ligand types. Structures of MeReO(η2-2-SC5H3N-3-SiMe)2 and (η5-Me5C5)Rh(η-2-SC5H3N-3-SiMe3) if(η1-2-SC5H3N-3-SiMe3)

Abstract Complexes of trimethylsilyl substituted pyridine-2-thiol with rhenium and rhodium have been prepared and structurally characterized. The reaction of methyltrioxorhenium with 3-trimethylsilylpyridine-2-thiol in toluene at 0 °C affords dark green plates of MeReO(η2-2-SC5H3N-3-SiMe3)2) (4). The reaction of [Cp∗RhCl2]2 with 3-trimethylsilylpyridine-2-thiol in THF, followed by extraction in hexanes and recrystalization yields Cp ∗ Rh (η 2 -2- SC 5 H 3 N -3- SiMe 3 ) (η 1 -2- SC 5 H 3 N -3- SiMe 3 ) (5). Crystal data: 4: monoclinic, P21/c, a=12.898(3), b=13.660(3), c=13.192(3) A , s=97.58(1)°, V=2303(1) A 3 , Z=4, D calc =1.010 g cm −3 ; structure solution and refinement based on 2297 reflections converged at a conventional residual of 0.0465. 5: orthorhombic, Pna2 1 , a=8.579(2), b=23.315(5), c=15.341(3) A , V=3068(2) A 3 , Z=4, D calc =1.305 g cm −3 ; 1455 reflections, R=0.0572.

Coordination chemistry of the tetrametalate core, {M4O16}: syntheses from [V2O2Cl2{(OCH2)2C(R)(CH2OH)}2] and structures of the mixed-metal cluster [V2Mo2O8(OMe)2{(OCH2)3CR}2]2– and the reduced cluster [V4O4(H2O)2(SO4)2{(OCH2)3CR}2]2–

The reactions of [Ph3PCH2Ph][VO2Cl2] with (HOCH2)3CR yield binuclear species of the type [V2O2Cl2{(OCH2)2C(R)(CH2OH)}2], which react in turn with [Bun4N]2[Mo2O7] to give the mixed-metal tetrametalates, [V2Mo2O8(OMe)2{(OCH2)3CR}2]2– and with [Bun4N]HSC4 and [Bun4N]3[H3V10O28] to yield the reduced tetravanadium clusters [V4O4(H2O)2(SO4)2{(OCH2)3CR}2]2–.