An efficient solvent-free protocol for the Buchwald–Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.

Treatment of Ru3(CO)12 with an equivalent of (2-phenyl-1H-inden-3-yl)dicyclohexylphosphine (1) and (2-pyridyl-1H-inden-1-yl)dicyclohexylphosphine (4) in refluxing heptane gave the novel trinuclear ruthenium clusters (μ3-η1:η2:η5–2-phenyl-3-Cy2PC9H4)Ru3(CO)8 (1c) and [μ2-η1–2-(pyridin-2-yl)-3-Cy2PC9H6]Ru3(CO)9 (4a), respectively, via C─H bond cleavage. (2-Mesityl-1H-inden-3-yl)dicyclohexylphosphine (2) reacted with Ru3(CO)12 in refluxing heptane to give the trinuclear ruthenium cluster [μ-2-mesityl-(3-Cy2PC9H5)](μ2-CO)Ru3(CO)9 (2c) via C─H bond cleavage and carbonyl insertion. 2-(Anthracen-9-yl)-1H–inden-3-yldicyclohexylphosphine (3) reacted with Ru3(CO)12 in refluxing heptane to give the dinuclear ruthenium cluster [μ2-η3:η3–2-(anthracen-9-yl)-3-Cy2PC9H6]Ru2(CO)5 (3a). The structures of 1c, 2c, 3a and 4a were fully characterized using IR and NMR spectroscopy, elemental analysis and single-crystal X-ray diffraction. These results suggest that the 2-aryl substituent on the indenyl ring has a pronounced effect on the reaction and coordination modes of Ru3(CO)12.

An easily available Pd(OAc)2/(2-(anthracen-9-yl)-1H-inden-3-yl) dicyclohexylphosphine/toluene/iPrOH/water catalytic system was developed, which shows high catalytic activity in the Suzuki–Miyaura cross-coupling reactions of a diverse array of aryl and heteroaryl chlorides with Pd loadings down to 0.01 mol%.

•A series of novel mono- and dinuclear gold(I) complexes were synthesized.•These complexes showed excellent aggregation-induced emission (AIE) properties.•These complexes showed three different mechanochromic behaviors.A series of novel carbazole-based mono- and dinuclear gold(I) complexes with various lengths of alkyl chains were synthesized and characterized using nuclear magnetic resonance spectroscopy, elemental analysis and single crystal X-ray diffractometry. Their aggregation-induced emission characteristics were investigated by ultraviolet/visible and photoluminescence spectroscopy. Their solid-state mechanochromic luminescence behavior was also studied by photoluminescence spectroscopy. All gold(I) complexes based on a carbazole scaffold structure exhibited excellent aggregation-induced emission properties. Luminogens 1 and 2 showed reversible mechanochromism phenomena involving luminescent color transformation from yellow–green to green. Luminogens 3 and 4 exhibited switchable mechanochromic luminescence behavior involving fluorescent color change from colorless to green. The solid-state fluorescence of luminogens 5 and 6 can be switched between weak and strong fluorescence by mechanical force stimulus, and this conversion is irreversible.Carbazole-based gold(I) complexes 1–6 all showed excellent AIE properties. In addition, luminogens 1 and 2 show reversible mechanochromism characteristics. Luminogens 3 and 4 exhibit switchable mechanochromic luminescence behaviors. Irreversible mechanofluorochromic phenomena were observed for luminogens 5 and 6.

An air-stable aryl substituted indenyl phosphine used in combination with Pd(OAc)2 provides a highly efficient catalyst for the Suzuki–Miyaura cross-coupling reaction of sterically hindered aryl halides with aryl boronic acids.

A new Buchwald-type diphosphine ligand has been developed for applications in Pd-catalyzed amination reactions towards the preparation of triarylamines. The catalyst can be used to perform the amination of a diverse array of aryl and heteroaryl chlorides.

We report the synthesis of 2-(anthracen-9-yl)-1H-inden-3-yl dicyclohexylphosphine and its use in palladium-catalyzed borylation/Suzuki–Miyaura cross-coupling reaction to prepare a variety of symmetrical and unsymmetrical biaryl compounds in excellent yield.

Phenylphosphinacalix[3]trifuran and supramolecular assemblies with palladium have been synthesized. Phenylphosphinacalix[3]trifuran affords turnover numbers as high as 3.05 × 107 in Suzuki–Miyaura cross-coupling reactions in pure water.

In this paper, five fluorene-based gold(I) complexes are synthesized and characterized. They exhibit typical aggregation-induced emission (AIE) properties or significant aggregate fluorescence change behaviors. Their thin-film and solid state fluorescence spectra are consistent with the luminescence of all luminogens in DMF–H2O mixtures with high water content. The emission color changes with different numbers of fluorene units. Among them, it is remarkable that luminogens 4 and 5 emit a bright white light in the thin-film and solid state. In addition, their thin-film absolute fluorescence quantum yields are also investigated. The results indicate the luminogen 4 gold(I) complex, with three fluorene units, exhibits the highest thin-film emission quantum yield, which is up to 65.42%.

Diels–Alder reactions based on arynes generated directly from bis-1,3-diynes have been developed. These reactions displayed good functional group compatibility and gave moderate to high yields under mild conditions. Such synthetic methodology can be effectively used for the synthesis of complicated ring compounds.Diels–Alder reactions based on arynes generated directly from bis-1,3-diynes have been developed. These reactions displayed good functional group compatibility and gave moderate to high yield under mild conditions. Such synthetic methodology can be effectively used for the synthesis of complicated ring compounds.

•Three novel trinuclear gold(I) complexes have been designed and synthesized.•These gold(I) complexes exhibit aggregation-induced emission characteristics.•The photoluminescence properties of these luminogens show off–on green fluorescence in response to mechanical grinding.Three novel trinuclear gold(I) complexes have been designed and synthesized. These gold(I) complexes exhibit aggregation-induced emission characteristics. Furthermore, the photoluminescence properties of these luminogens show off–on green fluorescence in response to mechanical grinding. The changing of weak multiple intermolecular C–H⋯F or π–π interactions, or the formation of aurophilic interactions are possibly responsible for their mechanochromism phenomena.Three novel gold(I) complexes have been synthesized, these luminogens exhibit aggregation-induced emission (AIE) behaviors and mechanochromic luminescence properties.

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.

We report the synthesis of 2-(3-sulfonatomesityl)-5-sulfonatoindenyl)dicyclohexylphosphine hydrate sodium salt and its use in palladium-catalyzed Suzuki–Miyaura and Sonogashira coupling reactions in water (and biphasic water–organic solvent mixtures) to prepare a variety of functionalized biaryls and aryl alkynes in excellent yield.

Some novel cycloaddition reactions based on benzyne and olefins have been developed. These reactions were performed in the absence of a transition metal catalyst, and they displayed good yields. These cycloaddition reactions of benzyne with olefins provide effective routes for synthesizing benzocyclobutenes, biaryl compounds and 9,10-dihydrophenanthrene derivatives.Some novel cycloaddition reactions based on benzyne and olefins have been developed. These reactions were performed in the absence of a transition metal catalyst.

Dinuclear indenyl ruthenium complexes were prepared and characterized using X-ray crystallography. Their crystal structures revealed the first examples of indenyl complexes containing an unusual η3 coordination mode with bonding through the junction carbon and the adjacent carbons of the five- and six-membered rings of the indenyl ligand.

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. 1H NMR and X-ray crystal structure studies reveal that there are intramolecular C–H⋯π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C–H⋯π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(CC) bands of these complexes in the neutral state and little effect on ν(CC) of these complexes in the oxidized state.

An easily available Pd(OAc)2/(2-mesitylindenyl)dicyclohexylphosphine/Me(octyl)3N+Cl−/K3PO4·3H2O catalytic system was developed and it shows high catalytic activity in the Suzuki–Miyaura cross-coupling reaction of a diverse array of aryl and heteroaryl chlorides in water. Notably, this catalytic system also works with ultra-low loading of the catalyst with high turnover numbers.

Thermal treatment of (1H-inden-3-yl)dicyclohexylphosphinium tetrafluoroborate (1) and (3-mesityl-1H-inden-3-yl)dicyclohexylphosphinium tetrafluoroborate (3) with tBuONa followed by [(η6-cymene)RuCl2)]2 in methanol gave the adduct {(η6-cymene)RuCl2[(1H-inden-3-yl)PCy2]} (6) and {(η6-cymene)RuCl2[(3-mesityl-1H-inden-3-yl)PCy2]} (7), respectively. Thermal treatment of (2-phenyl-1H-inden-3-yl)dicyclohexylphosphinium tetrafluoroborate (4) with tBuONa followed by [(η6-cymene)RuCl2)]2 or RuCl3·3H2O in methanol gave {Ru[κ(P):(η6-2-phenyl-1H-inden-3-yl)PCy2]Cl2} (8). Whereas (2-mesityl-1H-inden-3-yl)dicyclohexylphosphine (5) reacted with [(η6-cymene)RuCl2)]2 (in toluene) or RuCl3·3H2O (in ethanol) to afford {Ru[κ(P):(η6-2-mesityl-1H-inden-3-yl)PCy2]Cl2} (9). The molecular structures of complexes 6, 8 and 9 have been determined by single-crystal X-ray diffraction analysis. In addition, complexes 8 and 9 have been found to catalyze the acceptorless dehydrogenation of alcohols in toluene. 9 displayed high activity and different substrates, including cyclic and linear alcohols, were efficiently oxidized to ketones by using 2.0 mol% of catalyst.

Single crystal X-ray structural characterizations are recorded for an array of adducts of the form {AgX:[dppc][PF6]}n (n = 1 or 2), [dppc][PF6] = 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate, X = Cl, Br, NO3, NO2, C6H5CO2, CF3CO2. Synthetic procedures for all adducts are reported. All compounds have been fully characterised by elemental analysis and spectroscopic techniques. The structures in the solid state were found to depend on the nature of the counterion, for X = NO3, NO2, the complex being monomeric {[dppc-P,P′]Ag(NO3)2} or {[dppc-P,P′]Ag(NO2)}, for X = Cl, Br, C6H5CO2, CF3CO2, the complex is a dimer.Single crystal X-ray structural characterizations are recorded for an array of adducts of the form AgX:[dppc][PF6], [dppc][PF6] = 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate, X = Cl, Br, NO3, NO2, C6H5CO2, CF3CO2. The topology of the structures in the solid state was found to depend on the nature of the counterion.

Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested.

The reaction of [(η5-R2PC5H4)2Co][PF6] with (Me2S)AuCl (1:2) resulted in {[(η5-R2PC5H4)2Co](AuCl)2}[PF6] (R = Ph, Cy, or iPr). With a 1:1 ratio of [(η5-R2PC5H4)Co(η5-C5H5)][PF6] to (Me2S)AuCl, yellow crystalline {[(η5-R2PC5H4)Co(η5-C5H5)](AuCl)}[PF6] was produced. The reaction of {[(η5-Cy2PC5H4)Co(η5-C5H5)](AuCl)}[PF6] with phenyl acetylene gave {[(η5-Cy2PC5H4)Co(η5-C5H5)][Au(C≡C–Ph)]}[PF6], while the reaction of {[(η5-Cy2PC5H4)2Co](AuCl)2}[PF6] with phenyl acetylene produced the unusual ionic complex {[(η5-Cy2PC5H4)2Co][Au(C≡C–Ph)]2}[Au(C≡C–Ph)2]. The structure of this complex has been characterized by X-ray crystallography, and a possible pathway for its formation is suggested.

We report the synthesis of 2-(3-sulfonatomesityl)-5-sulfonatoindenyl)dicyclohexylphosphine hydrate sodium salt and its use in palladium-catalyzed Suzuki–Miyaura and Sonogashira coupling reactions in water (and biphasic water–organic solvent mixtures) to prepare a variety of functionalized biaryls and aryl alkynes in excellent yield.

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. 1H NMR and X-ray crystal structure studies reveal that there are intramolecular C–H⋯π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C–H⋯π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(CC) bands of these complexes in the neutral state and little effect on ν(CC) of these complexes in the oxidized state.

An easily available Pd(OAc)2/(2-mesitylindenyl)dicyclohexylphosphine/Me(octyl)3N+Cl−/K3PO4·3H2O catalytic system was developed and it shows high catalytic activity in the Suzuki–Miyaura cross-coupling reaction of a diverse array of aryl and heteroaryl chlorides in water. Notably, this catalytic system also works with ultra-low loading of the catalyst with high turnover numbers.

A new Buchwald-type diphosphine ligand has been developed for applications in Pd-catalyzed amination reactions towards the preparation of triarylamines. The catalyst can be used to perform the amination of a diverse array of aryl and heteroaryl chlorides.

An easily available Pd(OAc)2/(2-(anthracen-9-yl)-1H-inden-3-yl) dicyclohexylphosphine/toluene/iPrOH/water catalytic system was developed, which shows high catalytic activity in the Suzuki–Miyaura cross-coupling reactions of a diverse array of aryl and heteroaryl chlorides with Pd loadings down to 0.01 mol%.

An efficient solvent-free protocol for the Buchwald–Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.

Thermal treatment of (1H-inden-3-yl)dicyclohexylphosphinium tetrafluoroborate (1) and (3-mesityl-1H-inden-3-yl)dicyclohexylphosphinium tetrafluoroborate (3) with tBuONa followed by [(η6-cymene)RuCl2)]2 in methanol gave the adduct {(η6-cymene)RuCl2[(1H-inden-3-yl)PCy2]} (6) and {(η6-cymene)RuCl2[(3-mesityl-1H-inden-3-yl)PCy2]} (7), respectively. Thermal treatment of (2-phenyl-1H-inden-3-yl)dicyclohexylphosphinium tetrafluoroborate (4) with tBuONa followed by [(η6-cymene)RuCl2)]2 or RuCl3·3H2O in methanol gave {Ru[κ(P):(η6-2-phenyl-1H-inden-3-yl)PCy2]Cl2} (8). Whereas (2-mesityl-1H-inden-3-yl)dicyclohexylphosphine (5) reacted with [(η6-cymene)RuCl2)]2 (in toluene) or RuCl3·3H2O (in ethanol) to afford {Ru[κ(P):(η6-2-mesityl-1H-inden-3-yl)PCy2]Cl2} (9). The molecular structures of complexes 6, 8 and 9 have been determined by single-crystal X-ray diffraction analysis. In addition, complexes 8 and 9 have been found to catalyze the acceptorless dehydrogenation of alcohols in toluene. 9 displayed high activity and different substrates, including cyclic and linear alcohols, were efficiently oxidized to ketones by using 2.0 mol% of catalyst.

We report the synthesis of 2-(anthracen-9-yl)-1H-inden-3-yl dicyclohexylphosphine and its use in palladium-catalyzed borylation/Suzuki–Miyaura cross-coupling reaction to prepare a variety of symmetrical and unsymmetrical biaryl compounds in excellent yield.

An air-stable aryl substituted indenyl phosphine used in combination with Pd(OAc)2 provides a highly efficient catalyst for the Suzuki–Miyaura cross-coupling reaction of sterically hindered aryl halides with aryl boronic acids.