Mingsheng Huang

New compounds with extended structure latticesfrom the reactions of cuprous iodide with cyclicpolydisulfides

Abstract The reactions of CuI with 1,2,5,6-tetrathiacyclooctane, 1 SCH2CH2SSCH2CH2S and 1,2,5,6,9,10hexathiacyclododecane, 2 SCH2CH2SSCH2CH2SSCH2CH2S inacetonitrile solvent have yielded the new compounds [Cu2I2 (μ-SCH2CH2SSCH2CH2S) ] ∞, 3 and [CuI(μ-SCH2CH2SSCH2CH2SSCH2CH2S] ∞, 4 in yields of 75 and 61%, respectively. Both products werecharacterized crystallographically. Compound 3 contains a network of CuI double chains withstep ladder-like structures. The chains are linked by bridging η2-tetrathiacyclooctane ligands to form 2-dimensional sheets through coordination of the disulfidegroups to the copper atoms. Compound 4 contains isolated Cu2I2 groupswhich are linked by two bridging η2-hexathiacyclododecane ligands to form1-dimensional chains along the crystallographic b-direction.

Synthesis and X-ray crystal structure analysis of Fe2(CO)6(μ3-S)2Pd(bipy)

The reaction of Fe2(CO)6(μ-S2),1 withbis(dibenzylideneacetone)-palladium, Pd(dba)2, in the presence of 2,2′-bipyridine yielded the new compound Fe2(CO)6(μ3-S)2Pd(bipy),2 in good yield (66%). Compound2 was characterized by IR,1H NMR and single-crystal X-ray diffraction analyses. Compound2 contains a Pd(bipy) group that has been inserted into the S-S bond of1. Crystal data for2: space group P21/n,a=10.019(2) Å,b=25.414(5) Å,c=7.714(2) Å,β=90.26(2)°,Z=4, 1436 reflections,R=0.023.

New dithiocarbamate compounds of manganese carbonyl and a zinc polymer

Abstract The reaction of [EtO2CN=CS2C {N (H) CO2Et} {S2CN (H) CO2Et} ] , 1 with Mn2 (CO) 9NCMe yielded the dithiocarbamate complex Mn (CO) 4 [S2CN (H) CO2Et] , 2 which was characterized structurally in the form of its phosphine derivative Mn (CO) 3 (PMe2Ph) [S2CN (H) CO2Et] , 3. Compound 3 was found to contain a chelating dithiocarbamato ligand with a cis-positioned phosphine ligand. Compound 1 also reacts with zinc acetylacetonate to yield the zinc dithiocarbamate complex Zn (μ-S,S-S2CN (H) CO2Et) (μ-O,S-S2CN (H) CO2Et) , 4. Compound 4 forms a helical polymer in the solid state with the zinc ions linked by bridging dithiocarbamate ligands. Compound 1 appears to be a good source of the ethoxycarbonylthiocarbamate ligand.

Formation of a Stable Adduct of Ethoxycarbonyldithiocarbamic Acid and a Dimer of Ethoxycarbonyl Isothiocyanate

The reaction of ethoxyxcarbonyl isothiocyanate with water in the absence of a solvent has yielded the new compound [EtO2CN=CS2C{N(H)CO2Et}{S2CN(H)CO2Et}] (1) in 76% yield that has been isolated in a crystalline form that con-tains one equivalent of ethoxyxcarbonyl isothiocyanate. Compound 1 can be viewed as an adduct of a dimer of EtO2CN=C=S and the dithiocarbamic acid 2. Compound 1 dissociates in solution to yield 2 and free ethoxyxcarbonyl isothiocyanate. Compound 2 can be isolated chromatog-raphically, but it is slowly oxidized when allowed to stand in the open air to form the thiuram disulfide 3. Compounds 1 and 3 were characterized crystallographically. Compound 1 contains an imino-substituted dithietane ring with a dithiocarbamate substitutent bonded to one of the ring carbon atoms. Compound 3 is a thiuram disulfide which has C2 crystallographic symmetry.

Reaction of MeO2C(H)C=C=C(H)CO2Me with Ru3(CO)12. New diruthenium complexes with bridging carboxylate-substituted allene ligands

AbstractThe reaction of Ru3(CO)12 with MeO2C(H)C=C=C(H)CO2 Me has yielded two isomeric productsanti-Ru2(CO)6[μ-η3-η1-MeO2C(H)CCC(H)CO2Me],1 in 70% yield andsyn-Ru2(CO)6[μ-η3-η1-MeO2C(H)CCC(H)CO2Me],2 in 5% yield. Both compounds were characterized by single crystal X-ray diffraction analysis. Both products are diruthenium complexes with bridging di(carboxylate)allene ligands in which the oxygen atom of the carbonyl group of one of the carboxylate groupings is coordinated to one of the metal atoms. Compound1 isomerizes partially to2 at 68°C. Crystal Data for1: space group=P21/n,a=11.131(1) Å,b=10.228(2) Å,c=15.978(2) Å,β=102.01(1)°,Z=4, 1653 reflections,R=0.025; for2: space group=P

Alkyne Insertions into Metal-Metal Bonds. Synthesis of Heteronuclear Dimetalated Olefins by Insertion of MeO2CC.tplbond.CCO2Me into an Re-Fe Single Bond

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Catalytic Ring Opening of β-Propiothiolactones by Dirhenium and Dimanganese Carbonyl Complexes

,a=9.340(1) Å,b=14.925(4) Å,c=6.778(2) Å,α=99-02(2)°,β=104 62(2)°,γ=94.58(2)°,Z=2, 1857 reflections,R=0.027.