Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts

The synthesis of air‐ and moisture‐stable trinuclear mixed‐valence gold(I)/gold(0) clusters is described. They promote the catalytic carbonylation of amines under relatively mild conditions. The synthetic route leading to the trinuclear clusters involves a simple ligand exchange from the readily available μ³‐oxo‐[(Ph₃PAu)₃O]⁺ complex. This synthetic method paves the way for the preparation of a variety of mixed‐valence gold(I)/gold(0) polynuclear clusters. Moreover, the well‐defined nature of the complexes demonstrates that the catalytic process involves a rare example of a definite change of oxidation state of gold from Au⁰₂Au^I to Au^I₃.     

A persistent (amino)(ferrocenyl)carbene()

Deprotonation of N,N-diisopropyl-C-ferrocenylaldiminium triflate 2 cleanly leads to the corresponding 1,2-diamino-1,2-diferrocenylethene 3, the dimer of the desired (amino)(ferrocenyl)carbene. Fulvene 6, obtained by addition of the lithium salt of tetramethylcyclopentadiene to methoxyformamidinium methylsulfate 5, reacts with dicarbonylcyclopentadienylbromoiron(II), and with a mixture of FeCl(2) and Cp* lithium salt, affording the corresponding tetramethylferrocenylaldiminium salt 7, and nonamethylferrocenylaldiminium salt 8, respectively. Although the deprotonation of 7 gives a complex mixture of products, the treatment of 8 at -78 °C with sodium hexamethyldisilazide allowed for the isolation of the corresponding (amino)(ferrocenyl)carbene 9 as a yellow powder. However, even in the solid state, it is stable for less than 48 h at -20 °C. In addition to NMR spectroscopy, evidence for the carbene nature of 9 was found by a trapping experiment with sulfur that leads to the corresponding adduct 10, which was characterized by a single crystal X-ray diffraction study.     

Synthesis and anticancer properties of gold(I) and silver(I) N-heterocyclic carbene complexes

Bis(1,3-dimethylimidazol-2-ylidene)silver(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)silver(I) nitrate were prepared by reacting the corresponding imidazolium nitrate salts with silver oxide. Bis(1,3-dimethylimidazol-2-ylidene)gold(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)gold(I) nitrate salts were prepared via transmetallation of their silver precursors with chloro dimethylsulfide gold. The anticancer properties were determined using NCI-H460 lung cancer cells. Efficacy was established by comparison of the gold and silver compounds with cisplatin.     

环(烷基)(氨基)卡宾及其在烯烃复分解反应中的研究展望

烯烃复分解反应是形成碳碳双键的重要反应之一,其发展与结构明确的钌催化剂[L2X2Ru=CHR]中配体的创制密切相关.1999年,环二氨基卡宾配体的引入极大提高了催化剂的活性、稳定性以及官能团适用性.2005年,Bertrand等发展了一种比环二氨基卡宾具有更强给电子能力的配体──环(烷基)(氨基)卡宾(CAACs)配体,且卡宾中心α位为一季碳原子,这使得其空间环境与其他类型卡宾配体有很大差异.首先概述了CAACs配体的合成及性质,紧接着讨论了其在烯烃复分解催化反应中的研究进展,最后对该领域所存在的问题进行简要分析并对其发展作了展望.     

A Cyclic (Alkyl)(boryl)germylene Derived from a Cyclic (Alkyl)(amino)germylene

A cyclic (alkyl)(amino)germylene undergoes a ring expansion reaction with dibromomesitylborane (MesBBr₂) to afford a six‐membered dibromogermane derivative. In the presence of Lewis bases (PMe₃ or ^MeNHC), reduction of the latter with two equivalents of potassium graphite (KC₈) gives rise to cyclic (alkyl)(boryl)germylene–Lewis base adducts. Upon heating, the germylene—PMe₃ adduct reacts with H₂ to yield a germane, probably via a base‐free germylene featuring a small HOMO–LUMO gap.     

New structural motifs in the aggregation of neutral gold(I) complexes: structures and luminescence from (alkyl isocyanide)AuCN

The preparation and X-ray crystal structures of (CyNC)Au(I)CN, (n-BuNC)Au(I)CN, and (i-PrNC)Au(I)CN.0.5CH(2)Cl(2) are reported and compared with those of (MeNC)Au(I)CN and (t-BuNC)Au(I)CN, which were previously described. These linear molecules are all organized through aurophilic interactions into three structural classes: simple chains ((CyNC)Au(I)CN and (t-BuNC)Au(I)CN), side-by-side chains in which two strands make Au...Au contact with each other ((n-BuNC)Au(I)CN), and nets in which multiple aurophilic interactions produce layers of gold(I) centers ((i-PrNC)Au(I)CN and (MeNC)Au(I)CN). All of these five solids dissolve to produce colorless, nonluminescent solutions with similar UV/vis spectra. However, each of the solids displays a unique luminescence with emission maxima occurring in the range 371-430 nm.     

Decarboxylation of aromatic carboxylic acids by gold(I)-N-heterocyclic carbene (NHC) complexes

A recently isolated gold(I) complex, [Au(IPr)(OH)], permits the transformation of carboxylic acids to the corresponding decarboxylated gold(I)-aryl complex without the use of silver co-catalyst under mild reaction conditions.     

Synthesis, isolation and characterization of cationic gold(I) N-heterocyclic carbene (NHC) complexes

A number of cationic gold(I) complexes have been synthesized and found to be stabilized by the use of N-heterocyclic carbene ligands. These species are often employed as in situ-generated reactive intermediates in gold catalyzed organic transformations. An isolated, well-defined species was tested in gold-mediated carbene transfer reactions from ethyl diazoacetate.     

Bipyridyl/carbazolate silver(I) and gold(I) N-heterocyclic carbene complexes: A systematic study of geometric constraints and electronic properties

A series of silver(I) and gold(I) carbene complexes of the type [M(L)(2,2′-bipyridine)][PF₆] (L = 1-benzyl-3-(2-pyridylmethyl)benzimidazolylidene; M = Ag ( 1 ); M = Au ( 3 )) and [M(L)(carbazole)] (M = Ag ( 2 ); M = Au ( 4 )) were synthesized and analyzed using a range of spectroscopic and crystallographic techniques. Inspection of the solid-state structures of 1 , 2 and 4 revealed a number of intermolecular noncovalent interactions. In the solid-state structure adopted by 1 , π–π and Ag–Ag interactions directed the complexes to orient in a head-to-tail fashion. The photophysical properties were found to be influenced by the ancillary ligands in solution as well as in the solid-state. Calculations were performed to support the aforementioned structural and optoelectronic assignments.     

Thermolysis of gold(I) thiolate complexes producing novel gold nanoparticles passivated by alkyl groups

Thermolysis of gold(I) thiolate complex, [C14H29(CH3)3N][Au(SC12H25)2], at 180 degrees C for 5 h under an N2 atmosphere produces novel gold nanoparticles passivated by alkyl groups derived from the precursor complex, the TEM image of which shows spherical particles with average diameter 26 nm.     

Ultra-Long Lived Luminescent Triplet Excited States in Cyclic (Alkyl)(amino)carbene Complexes of Zn(II) Halides

The high element abundance and d¹⁰ electron configuration make Zn^II-based compounds attractive candidates for the development of novel photoactive molecules. Although a large library of purely fluorescent compounds exists, emission involving triplet excited states is a rare phenomenon for zinc complexes. We have investigated the photophysical and -chemical properties of a series of dimeric and monomeric Zn^II halide complexes bearing a cyclic (alkyl)(amino)carbene (cAAC) as chromophore unit. Specifically, [(cAAC)XZn(μ-X)₂ZnX(cAAC)] (X=Cl ( 1 ), Br ( 2 ), I ( 3 )) and [ZnX₂(cAAC)(NCMe)] (X=Br ( 4 ), I ( 5 )) were isolated and fully characterized, showing intense visible light photoluminescence under UV irradiation at 297 K and fast photo-induced transformation. At 77 K, the compounds exhibit improved stability allowing to record ultra-long lifetimes in the millisecond regime. DFT/MRCI calculations confirm that the emission stems from ³XCT/LE_cAAC states and indicate the phototransformation to be related to asymmetric distortion of the complexes by cAAC ligand rotation. This study enhances our understanding of the excited state properties for future development and application of new classes of Zn^II phosphorescent complexes.     

Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments

Discovered in 2005, cyclic (alkyl)(amino)carbenes (CAACs) are among the most nucleophilic (σ donating) and also electrophilic (π‐accepting) stable carbenes known to date. These properties allow them to activate a variety of small molecules and enthalpically strong bonds, to stabilize highly reactive main‐group and transition‐metal diamagnetic and paramagnetic species, and to bind strongly to metal centers, which gives rise to very robust catalysts. The most important results published up to the end of 2013 are briefly summarized, while the majority of this Review focuses on findings reported within the last three years.     

Intensely luminescent gold(I)-silver(I) cluster complexes with tunable structural features

A new series of isostructural, brilliantly luminescent gold-silver complexes having the formula [Au3(mu3-E)Ag(PPh2py)3](BF4)2 where E = O, S, Se and Ph2Ppy = 2-diphenylphosphinopyridine has been synthesized and characterized. The structural core of these complexes is a Au3Ag metallophilically linked tetrahedron with a group-16 atom functioning as a mu3-ligand capping the three gold atoms. In the solid state, pairs of clusters are joined by two unsupported aurophilic interactions. The emission energy changes strikingly in going from O (blue) to S (yellow) and Se (orange). The luminescence from the E = O system is the first to be reported for a gold(I) oxo system. Additionally, the luminescent 4-methylpyridyl analogue with E = S has been prepared and structurally characterized. For E = S, Se, the change in emission energy with mu3-bridging atom provides a sound basis for an LMMCT assignment of the excited state while lifetime measurements support its spin-forbidden nature. Frozen glass measurements indicate the presence of a higher-energy emitting state for these systems, and for the E = O system, either LMMCT or metal-centered cluster-based emission can be proposed.     

Silver(I) N-heterocyclic carbene halide complexes: A new bonding motif

Two new NHC silver halide salts have been synthesised and structurally characterised, and they show the two most common structural forms for such salts: the (NHC)AgX and the forms (both have a stoichiometry of 1 NHC:1 Ag:1 halide). A third new compound has been synthesised and structurally characterised: this compound has an unprecedented 2 NHC:1 Ag:1 halide stoichiometry and exhibits a planar arrangement of two coordinating NHCs, and a coordinating bromide about the central silver. The Ag-Br bond is long in the solid state and, together with solution NMR data, this suggests that a formulation of (NHC)₂Ag⁺Br⁻ might be more appropriate.     

Self-assembly of silver(I) and gold(I) N-heterocyclic carbene complexes in solid state, mesophase, and solution

The assembly of silver(I) and gold(I) complexes of functionalized N-heterocyclic carbenes (NHCs) of the type [M(C(n),amide-imy)(2)][anion] were studied, in which C(n),amide-imy stands for an NHC of imidazol-2-ylidene having one N-alkyl substituent (C(n)H(2n+1)) and one N-acetamido substituent, while the anions are Br(-), NO(3)(-), BF(4)(-) or PF(6)(-). A single crystal X-ray diffraction study reveals that self-assembly of [Ag(C(10),amide-imy)(2)][PF(6)] through Coulombic, hydrogen bonding, and hydrophobic interactions gives a lamellar structure with tubular architecture around the metal ion head core. Self-assembly of these functionalized NHC complexes also leads to the formation of the first example of thermotropic liquid crystals of silver(I)-NHCs and gels of gold(I)-NHC. Results from an infrared spectroscopy study show that the degree of chain motion in the gel state is smaller than that in the mesophase, yet comparable to that in the solid state. In addition, the technique of nuclear magnetic resonance diffusion ordered spectroscopy was found for the first time to be a good tool to study the phase transition of gels. Xerogels of gold(I)-NHCs display fibers, oriental lantern-shaped bundles of belts and helical fibers when observed under scanning electron and transmission electron microscopes.     

Dinuclear gold(I) complexes of bridging bidentate carbene ligands: synthesis, structure and spectroscopic characterisation

Eight dinuclear Au(i)-carbene complexes have been synthesized from various imidazolium-linked cyclophanes and related acyclic bis(imidazolium) salts, by treatment of the imidazolium salts with [Au(i)(SMe(2))Cl] in the presence of a carboxylate base. Single crystal structural studies showed that the Au(i)-carbene compounds contain dinuclear (AuL)(2) cations in which a pair of gold(i) centres are linked by a pair of bridging dicarbenoid ligands. Interestingly, the structural studies revealed short AuAu contacts of 3.0485(3)[Angstrom] and 3.5425(6)[Angstrom] in two of these complexes. NMR studies showed that the (AuL)(2) cations constructed from the cyclophane-based ligands retain a relatively rigid structure in solution, whilst those of the non-cyclophane ligand systems are fluxional in solution. The electronic absorption and emission spectra of the complexes in solution at room temperature were recorded and the complex with the shortest AuAu contact was found to emit intensely at 400 nm and more weakly at 780 nm upon excitation at 260 nm. The compounds with longer AuAu separations were not emissive under these conditions.     

A planar chiral six-membered cyclic (amino)(ferrocenyl)carbene and its sulfur adduct

A planar chiral ferrocene-fused cyclic aldimine was synthesized and a series of iminium salts were divergently prepared from it. The new carbene was generated from a salt by simple deprotonation with a strong base and identified by a carbene trapping experiment with sulfur. The sulfur adduct was fully characterized and its crystal structure implied that the new carbene would create an excellent chiral environment when used as a catalyst or a ligand in catalytic asymmetric synthesis.     

Synthesis, structural characterization, and theoretical studies of gold(I) and gold(I)-gold(III) thiolate complexes: quenching of gold(I) thiolate luminescence

The gold(I) thiolate complexes [Au(2-SC6H4NH2)(PPh3)] (1), [PPN][Au(2-SC6H4NH2)2] (2) (PPN = PPh3=N=PPh3), and [{Au(2-SC6H4NH2)}2(mu-dppm)] (3) (dppm = PPh2CH2PPh2) have been prepared by reaction of acetylacetonato gold(I) precursors with 2-aminobenzenethiol in the appropriate molar ratio. All products are intensely photoluminescent at 77 K. The molecular structure of the dinuclear derivative 3 displays a gold-gold intramolecular contact of 3.1346(4) A. Further reaction with the organometallic gold(III) complex [Au(C6F5)3(tht)] affords dinuclear or tetranuclear mixed gold(I)-gold(III) derivatives with a thiolate bridge, namely, [(AuPPh3){Au(C6F5)3}(mu2-2-SC6H4NH2)] (4) and [(C6F5)3Au(mu2-2-SC6H4NH2)(AudppmAu)(mu2-2-SC(6)H4NH2)Au(C6F5)3] (5). X-ray diffraction studies of the latter show a shortening of the intramolecular gold(I)-gold(I) contact [2.9353(7) or 2.9332(7) A for a second independent molecule], and short gold(I)-gold(III) distances of 3.2812(7) and 3.3822(7) A [or 3.2923(7) and 3.4052(7) A] are also displayed. Despite the gold-gold interactions, the mixed derivatives are nonemissive compounds. Therefore, the complexes were studied by DFT methods. The HOMOs and LUMOs for gold(I) derivatives 1 and 3 are mainly centered on the thiolate and phosphine (or the second thiolate for complex 2), respectively, with some gold contributions, whereas the LUMO for derivative 4 is more centered on the gold(III) fragment. TD-DFT results show a good agreement with the experimental UV-vis absorption and excitation spectra. The excitations can be assigned as a S --> Au-P charge transfer with some mixture of LLCT for derivative 1, an LLCT mixed with ILCT for derivative 2, and a S --> Au...Au-P charge transfer with LLCT and MC for derivative 3. An LMCT (thiolate --> Au(III) mixed with thiolate --> Au-P) excitation was found for derivative 4. The differing nature of the excited states [participation of the gold(III) fragment and the small contribution of sulfur] is proposed to be responsible for quenching the luminescence.