79384-10-4Relevant articles and documents
A Novel Anionic Gold-Indium Cluster Compound: Synthesis and Molecular and Electronic Structure
Gabba?, Fran?ois P.,Chung, Sai-Cheong,Schier, Annette,Krüger, Sven,R?sch, Notker,Schmidbaur, Hubert
, p. 5699 - 5705 (1997)
The insertion of InBr into the Au - Br bond of [(Ph3P)AuBr] in tetrahydrofuran (thf) in the presence of [(CH2-PPh2)2] (dppe) leads to the formation of an orange complex [(dppe)2Au]+[(dppe)2Au3In 3Br7(thf)]-, 2. Analytical, spectroscopic, and X-ray structural investigations showed that this product is an anionic analogue of a neutral chloride complex [(dppe)2Au3In3Cl6(thf)3], 1, prepared recently. Both complexes have an Au3In3 cluster core of approximate C2v symmetry with one extremely short Au-Au bond [Au1-Au3 2.575(1) ?] as part of a quasilinear array P1- Au1- Au3-P4, suggesting the presence of a bis(phosphine) complex of the neutral Au2 molecule as part of the cluster. The third gold atom (Au2) is then assigned oxidation state +1. To gain deeper insight into the structure and bonding of this novel class of gold cluster compounds, regarding mainly the peculiar cluster geometry, the charge distribution, and the oxidation states, a series of scalar relativistic all-electron density functional (DF) calculations on model systems has been performed. As a model for 1, the neutral cluster {Au3(PH3)4[InCl2(H 2O)]3} was studied. For the examination of the geometry of complexes 1 and 2, the cluster Au3(PH3),4I3 has been considered as a further simplified model, where iodine replaces the InX2(thf) units. Experimental and calculated cluster geometries agree satisfactorily, and the formal oxidation states of the gold atoms (0 for Au1 and Au3, +1 for Au2) could be confirmed, but for the In centers no interpretable differences of the Mulliken charges were found.
Development of a novel highly anti-proliferative family of gold complexes: Au(i)-phosphonium-phosphines
Rousselle, Benjamin,Bouyer, Florence,Bayardon, Jér?me,Laly, Myriam,Ghiringhelli, Fran?ois,Rousselin, Yoann,Bodio, Ewen,Malacea-Kabbara, Raluca
, p. 4880 - 4889 (2021/04/22)
A family of gold(i)-phosphonium-phosphine complexes was synthesized thanks to an efficient 5-step strategy, which involves a phospha-Fries rearrangement. It enables the facile variation of the phosphonium moiety. All the complexes along with a synthetic intermediate were fully characterized (a crystal structure was obtained for two of them). The antiproliferative properties of the six novel complexes were evaluated on three human cancer cell lines (A549, MDA-MB-231, and SW480) and compared to those of three benchmark anticancer drugs used in clinics (oxaliplatin, 5-fluorouracil, andpaclitaxel) and to a phosphonium-free gold(i) complex [Au(PPh3)Br]. All the gold(i) complexes, containing a phosphonium, displayed strong anti-proliferative properties. They were more efficient thanoxaliplatinand 5-fluorouracil, and one of the complexes was even more efficient thanpaclitaxel.
Photophysical properties of organogold(i) complexes bearing a benzothiazole-2,7-fluorenyl moiety: Selection of ancillary ligand influences white light emission
Mihaly, Joseph J.,Stewart, David J.,Grusenmeyer, Tod A.,Phillips, Alexis T.,Haley, Joy E.,Zeller, Matthias,Gray, Thomas G.
supporting information, p. 15917 - 15927 (2019/11/11)
Herein we report three new gold(i) complexes with a benzothiazole-2,7-fluorenyl moiety bound through a gold-carbon σ-bond and either an N-heterocyclic carbene or organophosphine as ancillary ligands. The complexes have been characterized by NMR spectroscopy, X-ray crystallography, high resolution mass spectrometry, elemental analysis, and static and time-resolved optical spectroscopy. These compounds absorb almost strictly in the ultraviolet region and exhibit dual-luminescence following three freeze-pump-thaw cycles in toluene. The selection of the ancillary ligand significantly influences the excited-state dynamics of the complexes. The two phosphine containing complexes have similar fluorescence and phosphorescence quantum yields leading to generation of white light emission. The carbene containing complex exhibits a higher fluorescence quantum yield compared to its phosphorescence quantum yield resulting in a violet emission. Extensive photophysical characterization of these compounds suggests that the phosphine complexes undergo intersystem crossing more efficiently than the carbene complex. This is supported by a three-fold increase in luminescence lifetime, a halving in fluorescence quantum yield, and an increase in intersystem crossing efficiency by 25 percent for the phosphine complexes. Density-functional theory calculations support these observations where the energy gap between the S1 and T2 states for the carbene is roughly twice that of the phosphine complexes. To our knowledge this is the first example of single-component mononuclear gold(i) complexes exhibiting non-excimeric state white light emission, although a similar phenomenon has been realized for gold(iii) aryl compounds. Further, the triplet lifetimes of all three complexes are on the order of one ms in freeze-pump-thaw degassed toluene. These molecules also exhibit delayed fluorescence; all of the complexes display diffusion-controlled rate constants for triplet-triplet annihilation. Strong excited-state absorption is observed from the singlet and triplet excited-states in these molecules as well. The singlet states have excited-state extinction coefficients on the order of 1.5 × 105 M-1 cm-1 and the triplet states have excited-state extinction coefficients on the order of 1.0 × 105 M-1 cm-1
Shape-Controlled Synthesis of Trimetallic Nanoclusters: Structure Elucidation and Properties Investigation
Kang, Xi,Xiong, Lin,Wang, Shuxin,Yu, Haizhu,Jin, Shan,Song, Yongbo,Chen, Tao,Zheng, Liwei,Pan, Chensong,Pei, Yong,Zhu, Manzhou
, p. 17145 - 17150 (2016/11/23)
The shape-controlled synthesis of metal nanoclusters (NCs) with precise atomic arrangement is crucial for tailoring the properties. In this work, we successfully control the shape of alloy NCs by altering the dopants in the alloying processes. The shape of the spherical [Pt1Ag24(SPhMe2)18] NC is maintained when [AuISR] is used as dopant. By contrast, the shape of Pt1Ag24is changed to be rodlike by alloying with [AuI(PPh3)Br]. The structures of the trimetallic NCs were determined by X-ray crystallography and further confirmed by both DFT and far-IR measurements. The shape-preserved [Pt1Au6.4Ag17.6(SPhMe2)18] NC is in a tristratified arrangement—[Pt(center)@Au/Ag(shell)@Ag(exterior)]—and is indeed the first X-ray crystal structure of thiolated trimetallic NCs. On the other hand, the resulting rodlike NC ([Pt2Au10Ag13(PPh3)10Br7]) exhibits a high quantum yield (QY=14.7 %), which is in striking contrast to the weakly luminescent Pt1Ag24(QY=0.1 %, about 150-fold enhancement). In addition, the thermal stabilities of both trimetallic products are remarkably improved. This study presents a controllable strategy for synthesis of alloy NCs with different shapes (by alloying heteroatom complexes coordinated by different ligands), and may stimulate future work for a deeper understanding of the morphology (shape)–property correlation in NCs.
Isomorphism in the structural chemistry of two-coordinate adducts of diphenyl(2-formylphenyl)phosphine and triphenylphosphine with gold(I) halides
Dunstan, Samuel P.C.,Healy, Peter C.,Sobolev, Alexandre N.,Tiekink, Edward R.T.,White, Allan H.,Williams, Michael L.
, p. 253 - 259 (2014/07/08)
Single crystal X-ray structure determinations are recorded for diphenyl(2-formylphenyl)phosphine gold(I) halides [Ph2(Ph-CHO)PAuX], X = Cl, Br and I, and for redeterminations of enhanced precision for triphenylphosphine gold(I) halides [Ph3PAuX], X = Cl, Br, I, and SCN0.91Br0.09. These complexes, other than [Ph 2(Ph-CHO)PAuCl], together with a diverse array of other structures, crystallize as an isomorphous series in the orthorhombic space group P2 12121 a = 9.804(1)-11.906(3), b = 11.771(2)-12.996(3) and c = 12.871(1)-14.169(3) ?. In these complexes, introduction of the formyl group results in only minor differences between the conformations of the two phosphine ligands and the corresponding Au-P, Au-X, and Au-P-X bond lengths and angles. The crystal packings of [Ph3PAuX] for X = Cl, Br, I and of [Ph2(Ph-CHO)PAuX] for X = Br and I show that, while these structures are isomorphous, different supramolecular synthons may be present, suggesting global packing considerations are all-important rather than specific supramolecular interactions. This is borne out by the different packing found for the centrosymmetric [Ph2(Ph-CHO)PAuCl] structure. Crystallization of the mixed anion structure [Ph 3PAuSCN0.91Br0.09] in the above P2 12121 lattice rather than the P21/c lattice reported for pure [Ph3PAuSCN] suggests that co-crystallization with bromide may impose constraints on packing considerations which favor crystallization in the P212121 lattice.
Exclusive synthesis of Au11(PPh3)8Br 3 against the Cl Analogue and the Electronic Interaction between Cluster Metal Core and Surface Ligands
Wu, Zhikun,Jin, Rongchao
, p. 12259 - 12263 (2013/09/23)
To goldly go: Exclusive Au11(PPh3)8Br 3 (see illustration) formation was obtained by a novel two-phase method, although the molar ratio of Br-/Cl- was 1:4, as identified by ESI-MS. Interestingly, the interaction of Au11 core electrons with the benzene π electrons of the phosphine ligands was revealed by NMR spectroscopy and optical absorption spectroscopic analyses. Copyright
Facile method of halogen exchange between Au(Cl)(L) and MeC(O)X (L = PPh3 and IPr; X = Br and I) via ?-bond metathesis supported by DFT calculation
Sanagawa, Atsushi,Kuniyasu, Hitoshi,Iwasaki, Takanori,Kambe, Nobuaki,Bobuatong, Karan,Ehara, Masahiro
supporting information, p. 831 - 832 (2013/09/02)
Complexes with the formula Au(X)(L) (X = Br and I; L = PPh3 and IPr) were conveniently prepared by a quite simple procedure using the treatment of Au(Cl)(L) with MeC(O)X and the subsequent evaporation under reduced pressure. The mechanistic study by DFT calculation with M06 functional supported that the reaction proceeded through σ-bond metathesis where Cl atom underwent a more roundabout course than Br atom did.
Gold and palladium combined for cross-coupling
Hashmi, A. Stephen K.,Lothschuetz, Christian,Doepp, Rene,Rudolph, Matthias,Ramamurthi, Tanuja D.,Rominger, Frank
, p. 8243 - 8246 (2010/02/27)
Gold and palladium-a unique liason: A study of the transmetalation abilities of organogold compounds builds the basis for a new class of cross-coupling reactions. Stable intermediates of gold catalysis deliver new complex products by a palladium-catalyzed coupling reaction, (see Scheme)
Transition metal alkynyl complexes by transmetallation from Au(CΞCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4)
Khairul, Wan M.,Fox, Mark A.,Zaitseva, Natasha N.,Gaudio, Maryka,Yufit, Dmitry S.,Skelton, Brian W.,White, Allan H.,Howard, Judith A. K.,Bruce, Michael I.,Low, Paul J.
, p. 610 - 620 (2009/05/06)
Facile acetylide transfer reactions take place between gold(i) complexes Au(CΞCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4) and a variety of representative inorganic and organometallic complexes MXLn
Halogen photoreductive elimination from gold(III) centers
Teets, Thomas S.,Nocera, Daniel G.
, p. 7411 - 7420 (2009/10/17)
Monomeric complexes of the type Au III (PR 3 )X 3 and bimetallic complexes of the type Au 2 I,III [μCH 2 (R 2 P) 2 ]X 4 and Au 2 III,III [μ-CH 2 (R 2 P) 2 ]X 6 (R = Ph, Cy, X = Cl - , Br - ) undergo facile photoelimination of halogen. M-X bond activation and halogen elimination is achieved upon LMCT excitation of solutions of Au III complexes in the presence of olefin chemical traps. As opposed to the typical one-electron redox transformations of LMCT photochemistry, the LMCT photochemistry of the Au III centers allows for theunprecedented (i) two-electron photoelimination of X 2 from a monomeric center and (ii) four-electron photoelimination of X 2 from a bimetalllic center. The quantum yields for X 2 photoproduction, in general, are between 10percent and 20percent for all species, showing only minimal dependence on the identity of the ligands about gold, or the nuclearity of the complex. Efficient X 2 photoelimination is observed in the absence of a chemical trap, providing a rare example of authentic, trap-free halogen elimination from a transitionmetal center.
