3878-45-3Relevant academic research and scientific papers
Dimetalla-heterocyclic carbenes: The interconversion of chalcocarbonyl and carbido ligands
Barnett, Harrison J.,Hill, Anthony F.
, p. 12593 - 12596 (2020)
The l-carbido complexes [Rh2(l-C)Cl2(PPh3)4] and [Rh2(l-C)Cl2(dppm)2] cleave CS2 to afford themonothiocarbonyl complexes [RhCl(CS)(PPh3)2] and [Rh2(l-CS)Cl2(dppm)2]. The latter reacts with dimethyl acetylenedicarboxylate (DMAD) to afford [Rh(l-CS)(l-DMAD)
Sulfur-based redox reactions in Mo3S74+ and Mo3S44+ clusters bearing halide and 1,2-dithiolene ligands: A mass spectrometric and density functional theory study
Llusar, Rosa,Polo, Victor,Velez, Ederley,Vicent, Cristian
, p. 8045 - 8055 (2010)
The gas phase fragmentation reactions of sulfur-rich [Mo3S 7Br6]2- (12-), [Mo3S 7(bdt)3]2- (22-), and [Mo 3S4(bdt)3]2- (32-) (bdt = benzenedithiolate) complexes have been investigated by electrospray ionization (ESI) tandem mass spectrometry and theoretical calculations at the density functional theory level. Upon collision induced dissociation (CID) conditions, the brominated 12- dianion dissociates through two sequential steps that involves a heterolytic Mo-Br cleavage to give [Mo3S 7Br5]- plus Br- followed by a two-electron redox process that affords [Mo3S5Br 5]- and diatomic S2 sulfur. Dianion [Mo 3S7(bdt)3]2- (22-) dissociates through two sequential redox processes evolving diatomic S 2 sulfur and neutral bdt to yield [Mo3S 5(bdt)3]2- and [Mo3S 5(bdt)2]2-, respectively. Conversely, dianion [Mo3S4(bdt)3]2- (32-), with sulfide instead of disulfide S22- bridged ligands, remains intact under identical fragmentation conditions, thus highlighting the importance of disulfide ligands (S22-) as electron reservoirs to trigger redox reactions. Regioselective incorporation of 34S and Se at the equatorial position of the Mo3S 7 cluster core in 12- and 22- have been used to identify the product ions along the fragmentation pathways. Reaction mechanisms for the gas-phase dissociation pathways have been elucidated by means of B3LYP calculations, and a comparison with the solution reactivity of Mo 3S7 and Mo3S4 clusters as well as closely related Mo/S/dithiolene systems is also discussed.
Chemistry of [CpCr(CO)3]2. Synthesis of Cp2Cr2(CO)4S, Cp2Cr2(CO)4S2, and Cp2Cr2(CO)5S2. Crystal structure and reactivity of Cp2Cr2(CO)4S2 and Cp2Cr2(CO)5S2
Goh, Lai Yoong,Hambley, Trevor W.,Robertson, Glen B.
, p. 1051 - 1057 (1987)
The instantaneous reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) in tetrahydrofuran or toluene with stoichiometric amounts of elemental sulfur produced Cp2Cr2(CO)4S (1) and Cp2Cr2(CO)5S2 (2) in near quantitative yields. A solution of 2 on standing 1 h at ambient temperature gave a mixture of Cp2Cr2(CO)4S2 (3) (76%) and 1. The transformation of the very labile complex 2 to 3 with the cleavage of a CO ligand thence to the linear multiple bonded Cr-S-Cr complex 1 with extrusion of a S atom and finally to Cp4Cr4S4 was demonstrated by a time-dependent NMR study at 30°C. When 2 was treated with CF3SO3CH3, one of the S atoms was immediately methylated, giving [Cp2Cr2(CO)5S2(CH 3)](SO3CF3) (4) as a fine black unstable solid, which decomposed in solution to give 1 and [Cp4Cr4S4(CH3)](SO 3CF3) (5). Complexes 1-3 have been characterized by elemental, spectral, and crystal structure analyses. The structure of 1 has been reported previously. Crystals of 2 are monoclinic, P21/n, with a = 11.638 (4) A?, b = 15.508 (5) A?, c = 9.825 (3) A?, β = 111.56 (2)°, and Z = 4. Crystals of 3 are monoclinic, P21/c, with a = 8.214 (1) A?, b = 11.464 (2) A?, c = 16.182 (3) A?, β = 92.44 (1)°, and Z = 4. The disulfur ligand bridges the two chromium centers asymmetrically μ-η1,η2 in 2 and symmetrically μ-η2 in 3. S-S distances [2.010 (4) A?, 2; 1.990 (1) A?, 3] are similar to those found in other transition-metal μ-S2 complexes. Metal atoms in both complexes exhibit 4:3, 7-coordination.
Crystal Structure of a Novel Tetranuclear Dithiocarboxylato Copper(I) Complex, 4(PPh3)2
Lanfredi, Anna Maria Manotti,Tiripicchio, Antonio,Camus, Annamaria,Marsich, Nazario
, p. 753 - 756 (1989)
The complex 4(PPh3)2> (1) was obtained by reaction of 4> with PPh3 in toluene in a ratio Cu:P=1:1.5.Its structure, determined by X-ray diffraction methods, shows a distorted trigonal-pyramidal arrangement of four copper atoms, with four surrounding dithiocarboxylate groups acting as triply bridging ligands.Three of the ligands bridge the apical and two basal metal atoms, the fourth bridges the three basal copper atoms.Crystals of (1) are triclinic, space group P, with Z=2 in a unit cell of dimensions a=12.995(3), b=15.783(4), c=16.002(5) Angstroem, α=83.66(2), β=102.97(3), and γ=93.38(2) deg.The structure has been solved by direct and Fourier methods and refined by block-matrix least squares to R=0.073 for 3978 observed reflections.
New Macrocyclic Complexes of Titanum(IV): Synthesis, Reactivity, and X-Ray Crystal Structure of the Trigonal Prismatic Ti(C22H22N4)Cl2, and Synthesis and Reactivity of its Peroxo, Disulphido, and Pyrocatecholato Derivatives
Goedken, Virgil L.,Ladd, Judith A.
, p. 142 - 144 (1982)
The new macrocyclic complex of titanum(IV), Ti(C22H22N4)Cl2 has been shown by X-ray crystallography to have a trigonal prismatic co-ordination geometry; the synthesis and reactivities of the peroxo, disulphido, and pyrocatecholato derivatives are discussed.
Formation of a methine carbon-to-rhenium σ bond in an oxorhenium(V)-benzothiazole complex
Schoultz,Gerber,Hosten
, p. 13 - 16 (2016)
The reaction of trans-[ReOCl3(PPh3)2] with 1-(1,3-benzothiazol-2-yl)-3-benzoylthiourea (Hbbt) in methanol led to the isolation of the complex [ReOCl2(cbt)(PPh3)] (1). It contains the monoanionic bidentate chelate N-((benzothiazol-2-ylamino)methylene)benzamide (cbt). The new ligand cbt is coordinated via a neutral ketonic oxygen and an anionic imino-acyl carbon atom, and was formed by the abstraction of the thionyl sulfur of Hbbt by a triphenylphosphine of the starting complex, with S = PPh3 also been formed as by-product. Compound 1 was characterized by elemental analysis, FTIR, proton NMR and single crystal X-ray diffraction.
Tungsten Ligand-Based Sulfur-Atom-Transfer Catalysts: Synthesis, Characterization, Sustained Anaerobic Catalysis, and Mode of Aerial Deactivation
Ward, James P.,Lim, Patrick J.,Evans, David J.,White, Jonathan M.,Young, Charles G.
, p. 16824 - 16828 (2020)
The synthesis, properties, X-ray structures, and catalytic sulfur-atom-transfer (SAT) reactions of W2(μ-S)(μ-S2)(dtc)2(dped)2 [1; dtc = S2CNR2-, where R = Me, Et, iBu, and Bn; dped = S2C2Ph22-] and W2(μ-S)2(dtc)2(dped)2 (2) are reported. These complexes represent the oxidized (1) and reduced (2) forms of anaerobic SAT catalysts operating through the bidirectional, ligand-based half-reaction (μ-S)(μ-S2) ? (μ-S)2 + S0. The catalysts are deactivated in air through the formation of catalytically inactive oxo complexes, (dtc)WO(μ-S)(μ-dped)W(dtc)(dped) (3), prompting us to recommend that group 6 SAT activity be assessed under strictly anaerobic conditions.
Reactions of triphenylphosphine with S4N3Cl
Prakash, Hari,Sisler, Harry H.
, p. 2200 - 2203 (1968)
It has been shown that S4N3Cl gives a complex series of reactions in which [(C6H5)3P=NP(C6H5) 3]Cl (I), [(C6H5)3PNH2]Cl (II), and [{(C6H5)3PN}3S]Cl3 (III) are produced. Compound III reacts with two molecules of triphenylphosphine giving [{(C6H5)3PN}3S]Cl 3·2P(C6H5)3 (IV), which crystallizes out of acetone with 2 moles of acetone. N-Chlorotriphenylphosphinimine is suggested as a probable intermediate in these reactions.
Reversible chalcogen-atom transfer to a terminal uranium sulfide
Smiles, Danil E.,Wu, Guang,Hayton, Trevor W.
, p. 12683 - 12685 (2014)
The reaction of elemental S or Se with [K(18-crown-6)][U(S)(NR2)3] (1) results in the formation of the new uranium(IV) dichalcogenides [K(18-crown-6)][U(η2-S2)(NR2)3] (2) and [K(18-crown-6)][U(η2-SSe)(NR2)3] (5). The further addition of elemental S to 2 results in the formation of [K(18-crown-6)][U(η3-S3)(NR2)3] (3). Complexes 2, 3, and 5 can be reconverted into 1 via the addition of R3P (R = Et, Ph), concomitant with the formation of R3P=E (E = S, Se).
Evidence for the formation of isothiocyanate during sulfurisation of phosphines and phosphites using xanthane hydride
Hanusek, Ji?í,Russell, Mark A.,Laws, Andrew P.,Page, Michael I.
, p. 417 - 419 (2007)
Contrary to a previous report, the sulfurisation of triphenylphosphines and trialkyl phosphites by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products but unstable thiocarbamoyl isothiocyanate which has been trapped with nucleophiles.
