121772-60-9Relevant academic research and scientific papers
(Fluoren-9-ylidene)methanedithiolato complexes of gold: Synthesis, luminescence, and charge-transfer adducts
Vicente, Jose,Gonzalez-Herrero, Pablo,Garcia-Sanchez, Yolanda,Jones, Peter G.,Bardaji, Manuel
, p. 7516 - 7531 (2008/10/09)
Piperidinium 9H-fluorene-9-carbodithioate and its 2,7-di-tert-butyl- substituted analogue [(pipH){S2CCH(C12H6R 2-2,7)}, R = H (1a), t-Bu (1b)] and 2,7-bis(octyloxy)-9H-fluorene-9- carbodithioic acid [HS2CCH(C12H6(OC 8H17)2-2,7), 2] and its tautomer [2,7-bis(octyloxy)fluoren-9-ylidene]methanedithiol [(HS)2C=C(C 12H6(OC8H17)2-2,7), 3] were employed for the preparation of gold complexes with the (fluoren-9-ylidene)methanedithiolato ligand and its substituted analogues. The gold(I) compounds Q2[Au2{μ-K2-S,S-S 2C=C12H6R2-2,7)}2], where Q+ = PPN+ or Pr4N+ for R = H (Q24a) or Q+ = Pr4N+ for R = OC 8H17 [(Pr4N)24c], were synthesized by reacting Q[AuCl2] with 1a or 2 (1:1) and excess piperidine or diethylamine. Complexes of the type [{Au(PR′3)} 2{,u-κ2-S,S-S2C=C(C12H 6R2-2,7)}2] with R = H and R′ = Me (5a), Et (5b), Ph (5c), and Cy (5d) or R = t-Bu and R′ = Me (5e), Et (5f), Ph (5g), and Cy (5h) were obtained by reacting [AuCl(PR'3)] with 1a,b (1:2) and piperidine. The reactions of 1a,b or 2 with Q[AuCl4] (2:1) and piperidine or diethylamine gave Q[Au{κ2-S,S-S 2C=C(C12H6R2-2,7)}2] with Q+ = PPN+ for R = H [(PPN)-6a], Q+ = PPN + or Bu4N+ for R = t-Bu (Q6b), and Q + = Bu4N+ for R = OC8H17 [(Bu4N)6c]. Complexes Q6a-c reacted with excess triflic acid to give [Au{κ2-S,S-S2C=C(C12H6R 2-2,7)}{κ2-S,S-S2CCH(C12H 6R2-2,7)}] [R = H (7a), t-Bu (7b), OC8H 17 (7c)]. By reaction of (Bu4N)6b with PhlCl2 (1:1) the complex Bu4N[AuCl2{κ2-S,S- S2C= C(C12H6(t-Bu)2-2,7)}] [(Bu 4N)8b] was obtained. The dithioato complexes [Au{SC(S)CH(C 12H8)}{PCy3)] (9) and [Aun(S 2-CCH(C12H8)}n] (10) were obtained from the reactions of 1a with [AuCl(PCy3)] or [AuCl(SMe 2)], respectively (1:1), in the absence of a base. Charge-transfer adducts of general composition Q[Au{κ2-S,S-S 2C=C(C12H6R2-2,7)}2]· 1.5TCNQ·xCH2Cl2 [Q+ = PPN+, R = H, x = 0 (11a); Q+ = PPN+, R = t-Bu, x = 2 (11b); Q+ = Bu4N+, R = OC8H17, x = 0 (11c)] were obtained from Q6a-c and TCNQ (1:2). The crystal structures of 5c·THF, 5e·2/3CH2Cl2, 5g·CH 2Cl2, (PPN)6a·2Me2CO, and 11b were solved by X-ray diffraction studies. All the gold(I) complexes here described are photoluminescent at 77 K, and their emissions can be generally ascribed to LMMCT (Q24a,c, 5a-h, 10) or LMCT (9) excited states.
Organometallic gold(III) compounds as catalysts for the addition of water and methanol to terminal alkynes
Casado, Raquel,Contel, Maria,Laguna, Mariano,Romero, Pilar,Sanz, Sergio
, p. 11925 - 11935 (2007/10/03)
Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(III) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol% with respect to the alkyne), Thus, compounds of the general formula Q[AuRCl3], Q[AuR2Cl2], [AuRCl2]2, and [AuR2Cl]2, (Q = BzPPh3+, PPN: N(PPh3)2+ or N(Bu)4+; R = C6F5 or 2,4,6-(CH3)3C6H2) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C6F 5)2Cl]2 and phenylacetylene that was followed by variable temperature 1H, 19F{1H}, COSY 19F{1H}-19F{1H}, and 2H{1H} NMR experiments. Compound [Au(C6F 5)2Cl]2 is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.
Mesityl gold(III) complexes. X-ray structure of mononuclear [Au(mes)2Cl(PPh3)] and the dimer [Au(mes)2Cl]2
Contel, María,Edwards, Andrew J.,Garrido, Julián,Hursthouse, Michael B.,Laguna, Mariano,Terroba, Raquel
, p. 129 - 136 (2007/10/03)
The reaction between PPN[AuCl4] and [Hg(mes)2] gives the anionic complex cis-PPN[Au(mes)2Cl2] (1) and [Hg(mes)Cl] as side-product. Complex 1 is a precursor to other compounds both neutral and cationic. Removal o
Complexes with S-donor ligands. 7. New 1,1-ethylenedithiolato complexes of thallium(I), Gold(I), and gold(III): Syntheses, structure, and molecular cubic hyperpolarizabilitiest
Vicente, Jose
, p. 5018 - 5026 (2008/10/08)
β-Diketonato complexes [Tl{CH{C(O)R}2}] or PPN[Au{CH{C(O)R}2}2] [where PPN = (Ph3P)2N] react with an excess of CS2 to give, respectively, [Tl2{S2C=C{C(O)R}2
