- Alkynyl-Protected Au23 nanocluster: A 12-electron system
-
A 23-gold-atom nanocluster was prepared by NaBH4-mediated reduction of a solution of PhC≡CAu and Ph3PAuSbF6 in CH2Cl2. The cluster composition was determined to be [Au23(PhC≡C)9(Ph3P)6]2+ and single-crystal X-ray diffraction revealed that the cluster has an unprecedented Au17 kernel protected by three PhC2-Au-C2(Ph)-Au-C2Ph motifs and six Ph3P groups. The Au17 core can be viewed as the fusion of two Au10 units sharing a Au3 triangle. Electronic structure analysis from DFT calculations suggests that the stability of this unusual 12-electron cluster is a result of the splitting of the superatomic 1D orbitals under D3h symmetry of the Au17 kernel. The discovery and determination of the structure of the Au23 cluster demonstrates the versatility of the alkynyl ligand in leading to the formation of new cluster compounds.
- Wan, Xian-Kai,Yuan, Shang-Fu,Tang, Qing,Jiang, De-En,Wang, Quan-Ming
-
-
Read Online
- Au19 nanocluster featuring a v-shaped alkynyl-gold motif
-
A novel Au19 nanocluster with a composition of [Au19(PhC≡C)9(Hdppa)3](SbF6)2 was synthesized (Hdppa = N,N-bis(diphenylphosphino)amine). Single crystal X-ray structural analysis reveals that the cluster comprises a centered icosahedral Au13 core hugged by three V-shaped PhC≡C-Au-C≡C(Ph)-Au-C≡CPh motifs. Such motif is observed for the first time in an alkynyl-protected gold nanocluster. The Au19 cluster shows two main optical-absorption bands at 1.25 and 2.25 eV, confirmed by time-dependent density functional theory. Orbital analysis indicates that PhC≡C- groups can actively participate in the frontier orbitals of the whole cluster. The new Au19 cluster and the novel alkynyl-gold motif open the door to understanding the alkynyl-gold interface and discovering many potential members of this new class of gold clusters.
- Wan, Xian-Kai,Tang, Qing,Yuan, Shang-Fu,Jiang, De-En,Wang, Quan-Ming
-
-
Read Online
- Synthesis, structure and spectroscopic properties of bis(triphenylphosphane)iminium (phenylacetylido)(cyanido)aurate(I) monoacetone monohydrate, (PPN)[Au(CN)(CCC6H5)]·H2O·(CH3)2CO and bis(triphenylpho
-
Two new compounds containing the (acetylido)(cyanido)aurate(I) anion are reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane)iminium, are reported as a product containing a water molecule and an acetone molecule for the
- Alsalme, Ali,Jaafar, Mohammed,Liu, Xue,Dielmann, Fabian,Hahn, F. Ekkehardt,Al-Farhan, Khalid,Reedijk, Jan
-
-
Read Online
- A Near-Infrared-Emissive Alkynyl-Protected Au24 Nanocluster
-
An alkynyl-protected gold nanocluster [Au24(CΞCPh)14(PPh3)4](SbF6)2 has been prepared by a direct reduction method. Single-crystal X-ray diffraction reveals that the molecular structure contains a Au22core that is made of two Au13-centered cuboctahedra that share a square face. Two staple-like PhCΞCAuCΞCPh motifs are located around the center of the rod-like Au22core. This Au24 nanocluster is highly emissive in the near-infrared region with λmax=925nm and the nature of the HOMO-LUMO transition is investigated by time-dependent DFT calculations. Good as gold: An alkynyl-protected gold nanocluster [Au24(CΞCPh)14(PPh3)4](SbF6)2 is reported which contains a Au22core composed of two Au13 centered cuboctahedra that share a square face. Two staple-like PhCCAuCCPh motifs are located around the center of the rod-like Au22core. The Au24 nanocluster is highly emissive in the near-infrared region (λmax=925nm). Atom colors: Au=orange; C=gray.
- Wan, Xian-Kai,Xu, Wen Wu,Yuan, Shang-Fu,Gao, Yi,Zeng, Xiao-Cheng,Wang, Quan-Ming
-
-
Read Online
- 1,1-Phosphaboration of CC and CC bonds at gold
-
The phosphine-borane iPr2P(o-C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3) was found to react with gold(i) alkynyl and vinyl complexes via an original 1,1-phosphaboration process. Zwitterionic complexes resulting from Au to B transmetallation have been authenticated as key intermediates. X-ray diffraction analyses show that the alkynyl-borate moiety remains pendant while the vinyl-borate is side-on coordinated to gold. According to DFT calculations, the phosphaboration then proceeds in a trans stepwise manner via decoordination of the phosphine, followed by anti nucleophilic attack to the π-CC bond activated by gold. The boron center acts as a relay and tether for the organic group. This journal is
- Theulier, Cyril A.,García-Rodeja, Yago,Saffon-Merceron, Nathalie,Miqueu, Karinne,Bouhadir, Ghenwa,Bourissou, Didier
-
supporting information
p. 347 - 350
(2021/01/25)
-
- Synthesis and molecular recognition studies on small-molecule inhibitors for thioredoxin reductase
-
Thioredoxin reductase (TrxR), which is overexpressed in many aggressive cancers, plays a crucial role in redox balance and antioxidant function, including defense of oxidative stress, control of cell proliferation, and regulation of cell apoptosis. Deactivation of TrxR can destroy the homeostasis of the cancer cells, inducing elevation of reactive oxygen species (ROS) levels and the oxidation of enzymatic substrates. Here, we synthesized and identified a new gold(I) small molecule (D9) that possesses two strong electron-donating moieties, i.e., 4-methylphenyl alkynyl and thionyldiphenyl phosphine, exhibiting an enhanced p-π conjunction effect. The resulting compound shows the increased soft Lewis acids and the stability of gold(I). And we demonstrated that D9 could efficiently and specifically inhibit the activity of TrxR in vitro and in vivo, and it could effectively avoid the ligand exchange with albumin that was one of the most abundant proteins in blood. We believe that these comprehensive studies on the relationship between the structure and performance will provide inspiring information on the precise synthesis and design of new compounds for targeting TrxR.
- Zhang, Di,Xu, Zhonghe,Yuan, Jia,Zhao, Ying-Xi,Qiao, Zeng-Ying,Gao, Yu-Juan,Yu, Guang-Ao,Li, Jingyuan,Wang, Hao
-
p. 8132 - 8139
(2014/12/10)
-
- Pyridyl gold(I) alkynyls: A synthetic, structural, spectroscopic, and computational study
-
Planar neutral organometallic complexes have the potential to be exploited as building blocks for the construction of self-assembled nanoscale materials. We report the synthesis and first structural characterization of planar pyridyl gold(I) alkynyl complexes. Stable isolable complexes are only obtained when electron-rich pyridine ligands such as 4-(dimethylamino)pyridine or 4-aminopyridine are incorporated into the complexes. X-ray crystallography confirms that the pyridyl gold(I) alkynyls are neutral, linear, two-coordinate complexes. Furthermore, these gold(I) molecules form dimers in the solid state. However, no aurophilic interactions are observed to stabilize the solid-state structures. Density functional theory (DFT) calculations have been employed to model the electronic structure and thermodynamics of formation for selected complexes.
- Kilpin, Kelly J.,Horvath, Raphael,Jameson, Geoffrey B.,Telfer, Shane G.,Gordon, Keith C.,Crowley, James D.
-
p. 6186 - 6195
(2011/02/16)
-
- Reactions of gold(I) acetylides with l,1'-diisocyanoferrocene: From orthodox to unorthodox behavior
-
1,1'-Diisocyanoferrocene (1) reacts with the gold(I) acetylides [Au(C≡C-p-C6H4R)]n (2a R = CF3, 2b R = H, 2c R = OMe, 2d R = NMe2) to afford the respective dinuclear gold complexes [{Au(C≡C-p- C6H4R)}2(μ-1)] (3), whose aurophilic aggregation in the solid state depends on the nature of the substituent R. The product of the reaction of 1 with [Au(C≡C-Fc)] n (2e, Fc = ferrocenyl) is the hexanuclear gold cluster [(Fc-C≡C-Au-C≡N-C5H4)Fe{C5H 4-N=C(Au)-C≡C-Fc}]3, which is composed of three subunits 4 and exhibits an unusual arrangement of gold atoms. The formation of (4)3 is based on a different specific reaction of the two chemically equivalent functional groups of 1 with 2e, viz., coordination and 1,1-insertion. This schizoid behavior apparently is a novel variant of induced reaction asymmetry and constitutes a new phenomenon in chemistry. The reaction of 2e with l,1'-bis(diphenylphosphanyl)ferrocene (5) affords the expected [(Au-C≡C-Fc)2(μ-5)] (6), which does not exhibit aurophilic interactions.
- Siemeling, Ulrich,Rother, Dag,Bruhn, Clemens
-
p. 6419 - 6426
(2009/05/30)
-
- Chemistry of the Group 1B Metals. XVII. Preparation of Some Gold(I) Acetylide Complexes Containing Group 5 Donor Ligands: Crystal and Molecular Structures of Au(C2C6F5)(PPh3)
-
Experimentally convenient syntheses of a series of gold(I) acetylide complexes containing tertiary phosphines include reactions between AuCl(PR3) and alk-1-ynes, either in diethylamine in the presence of copper(I) halides, or with methanol/sodium methoxide.Yields are good to excellent; several compounds are light-sensitive, and react violently with chlorinated solvents.The crystal structure of Au(C2H6F5)(PPh3) has been determined.It is monomeric, with almost linear two-coordinate Au: Au-C 1.993(14), Au-P 2.274(3), CC 1.197(16) Angstroem.Crystals are monoclinic, space group P21/c, with a 16.104(2), b 8.653(1), c 17.560(3) Angstroem, β 112.98(1) deg, Z 4; 1761 data with I > 2.5?(I) were refined to R, Rw = 0.033, 0.034.
- Bruce, Michael I.,Horn, Ernst,Matisons, Janis G.,Snow, Michael R.
-
p. 1163 - 1170
(2007/10/02)
-