- Photoinduced Isomerization-Driven Structural Transformation between Decanuclear and Octadecanuclear Gold(I) Sulfido Clusters
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Upon photoirradiation, isomerization of the ligands, 1,2-bis(diphenylphosphino)ethene (dppee) from the cis to the trans form in polynuclear gold(I) sulfido clusters, led to the structural transformation of the decagold(I) cluster to the octadecagold(I) cl
- Yao, Liao-Yuan,Yam, Vivian Wing-Wah
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- Photochemical reactivity of two gold(I) dinuclear complexes, cis/trans-(AupNBT)2dppee: Isomerization for the cis-(AupNBT) 2dppee isomer, radical substitution for trans-(AupNBT) 2dppee
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Two complexes, cis (1) and trans (2) (AupNBT)2dppee (pNBT = p-nitrobenzenethiol; dppee = bis(diphenylphosphino)ethylene) have been synthesized and characterized. X-ray diffraction studies reveal that cis-(AupNBT)2dppee has an intramolecular gold-gold distance of 3.0036(3) ? while the trans-(AupNBT)2dppee crystal is a dimer with an intermolecular gold-gold distance of 3.1201(4) ?. We have used UV-Vis spectroscopy, 1H NMR, and 31P {1H} NMR to investigate the photochemical reactivity of both complexes. In a range of organic solvents with λ > 230 nm cis-(AupNBT)2dppee readily isomerizes to the trans isomer. Under these same conditions, the trans isomer does not isomerize to cis-(AupNBT)2dppee, but undergoes a photochemical substitution reaction. In chlorinated solvents (CH 2Cl2, CH3Cl) trans-(AupNBT)2dppee reacts to form trans-(AuCl)2dppee (3) which crystallizes into an extended chain of molecules linked via intermolecular gold-gold distances of 3.0203(2) ?. TDDFT calculations support the observed experimental results. We propose that at high energies the reaction is initiated by chlorine radicals from direct photolysis of the solvent. At longer wavelengths the excited state of the metal complex is the photoactive species, abstracting a chlorine radical from the solvent.
- Foley, Janet B.,Herring, Angela,Li, Bo,Dikarev, Evgeny V.
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p. 300 - 310
(2013/01/13)
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- Structure and photochemical isomerization of the dinuclear gold(I) halide bis(diphenylphosphanyl)ethylene complexes: Correlation between quantum yield and aurophilicity
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The crystal structures for cis-(Ph2PCH=CHPPh2)(AuI) 2 and trans-(Ph2PCH=CHPPh2) (AuI)2 are reported. The structure of cis-(Ph2PCH=CHPPh2)(AuI) 2 reveals a short intramolecular Au-Au distance of 2.9526(5) A, while the structure of trans(Ph2PCH=CHPPh2)(AuI) 2 shows intermolecular Au-Au distances of 3.2292(7) A. Structural data for the iodide complexes are compared to previously reported crystal structural data for cis- and trans-(Ph2PCH=CHPPh 2)(AuCl)2 and dppbz(AuCl)2. The quantum yields for the photochemical isomerization of cis-(Ph2PCH=CHPPh 2)(AuX)2 with 334-nm light, Φ(cis→trans). are 0.204, 0.269, and 0.363 for X = Cl, Br, and I, respectively. Prior results from ab initio calculations on the model cis- and trans-Au2X 2C2H2(PH2)2 complexes aid in the interpretation of the correlation between the quantum yield for isomerization and the calculated aurophilic attraction potential V(R e). Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Foley, Janet B.,Gay, Stanley E.,Vela, Michael J.,Foxman, Bruce M.,Bruce, Alice E.,Bruce, Mitchell R. M.
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p. 4946 - 4951
(2008/03/30)
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- Polymeric and macrocyclic gold(I) complexes with bridging dithiolate and diphosphine ligands
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The reaction of digold(I) diphosphine complexes [Au2(O2CCF3)2(μ-Ph2P-X -PPh2)] with dithiols HS-Y-SH can give either macrocyclic complexes [Au2(μ-S-Y-S)(μ-Ph2P-X-PPh2)] or polymeric complexes [Au2(μ-S-Y-S)(μ-Ph2P-X-PPh2)] n. The structures of the macrocyclic complex [Au2{μ-(S-4-C6H4)2S}{μ -Ph2P(CH2)4PPh2}], and the polymeric complexes [Aun{μ-(S-CH2CO2CH2CH 2O)2-1,4-C6H4}n(μ- trans-Ph2PCH{double bond, long}CHPPh2)n] and [Aun{μ-(S-CH2CO2CH2CH 2O)2-1,5-C10H6}n(μ -trans-Ph2PCH{double bond, long}CHPPh2)n] have been determined. Evidence is presented that the complexes exist primarily as macrocycles in solution and that, in favorable cases, ring-opening polymerization occurs during crystallization.
- Hunks, William J.,Jennings, Michael C.,Puddephatt, Richard J.
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p. 3605 - 3616
(2008/10/09)
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- Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 114. Ditungsten-Digold Compounds having two W(CC6H4Me-4)(CO)2(η5-C2B9H9Me2) Fragments linked by AuP(Ph)2(CH2)n(Ph)2PAu (n = 2-6) Groups
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Treatment of 1 equivalent of the reagent CR)(CO)2(η5-C2B9H9Me2)> (R = C6H4Me-4), in the presence of TlBF4, with 0.5 equivalent of the compounds > (n = 2-6) in CH2Cl2 affords the complexes (CO)4(η5C2B9H9Me2)2>.The crystal structure of the species with n = 4 has been determined by X-ray crystallography, confirming that the molecule has two RCW(CO)2(η5-C2B9H9Me2) fragments bridged by an AuP(Ph)2CH2CH2CH2CH2(Ph)2PAu unit, with a centre of inversion at the midpoint of the chain of methylene groups.The W-Au bonds are asymmetrically bridged by the p-tolylmethylidyne ligands .In a similar manner, the compounds 5-C2B9H9Me2)2> have been prepared from reactions between the gold compounds and the salt CR)(CO)2(η5-C2B9H9Me2)>.Addition of (cod = cycloocta-1,5-diene) to the complexes (CO)4(η5C2B9H9Me2)2> affords the chain cluster compounds 3-CR)2(μ-Ph2P(CH2)nPPh2>(CO)4(cod)2(η5-C2B9H9Me2)2>.The NMR data (1H, 13C-, 31P- and 11B- for the new complexes are reported and discussed.
- Goldberg, Justin E.,Mullica, Donald F.,Sappenfield, Eric L.,Stone, F. Gordon A.
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p. 2495 - 2502
(2007/10/02)
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- Synthesis and Structure of μ--bis
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The 1 : 2 ligand: Au(I) complex was prepared by reduction of Au(III) to Au(I) with 2,2'-thiodiethanol followed by reaction with an excess of ligand, and thus differs from the product characterized previously from direct reduction of Au(III) with the ligand.Infrared band assignments for ν(Au-P) and ν(Au-Cl) of the present complex are 352 and 322 cm-1, respectively.Assignments for ν(Au-P) and ν(Au-Cl) of 347 and 323 cm-1, respectively, for the complex of the cis ligand, which are more consistent than present literature values, are reported also.The crystal structure of the complex has been determined from diffractometer data and refined to R = 0.031 based on 2104 observed reflections /= 3?(I)>.The molecule sits on an inversion centre in space group C2/c, thus the trans geometry of the ligand and of the complex are rigorously reflected in the crystallographic results.The gold atom is linearly co-ordinated with normal Au-Cl and Au-P bond lengths of 2.291(2) and 2.235(2) Angstroem, respectively.A short intermolecular Au...Au contact of 3.043(1) Angstroem is observed.
- Eggleston, Drake S.,McArdle, James V.,Zuber, Gary E.
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p. 677 - 680
(2007/10/02)
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