The geometry and the energy of conformers of PnHn+2(n=2-9) have been studied with PM3 method. It is concluded that gauche interaction between adjacent lone electron pairs and gauche interaction between P-H bond with a...The geometry and the energy of conformers of PnHn+2(n=2-9) have been studied with PM3 method. It is concluded that gauche interaction between adjacent lone electron pairs and gauche interaction between P-H bond with adjacent P-P bond are important for predicting the stable conformer of open-chain phosphoanes.展开更多
The coordination chemistry of chalcogenide ligands has always attracted significant interest in the field of inorganic chemistry,especially for soft metals such as those of group 11.Despite the scarcity of research on...The coordination chemistry of chalcogenide ligands has always attracted significant interest in the field of inorganic chemistry,especially for soft metals such as those of group 11.Despite the scarcity of research on phosphane tellurides,we report on the synthesis and characterisation of five novel silver complexes containing the phosphane telluride ligand,TeP(iPr)_(3),along with other ancillary ligands such as mono or diphosphanes.Spectroscopic studies were performed to investigate the behaviour of these complexes,including their redox properties,as demonstrated by the 1,1′-diphenylphosphaneferrocene(dppf)silver derivatives.Additionally,these complexes showcase remarkable rapid interchange equilibrium,revealing silver species with distinctive Ag_(2)Te_(2) cores and a combination of bridging and terminal TeP(iPr)_(3) ligands.A promising avenue for further investigation and potential applications emerges.展开更多
1 Results Over the past few years significant research has been directed toward the development of organic materials for potential application in molecular photonic devices[1] and the development of sensors[2].Interes...1 Results Over the past few years significant research has been directed toward the development of organic materials for potential application in molecular photonic devices[1] and the development of sensors[2].Interest in these materials is primarily due to the infinite numbers of possible molecular structures with the desired properties,by virtue of the tremendous capabilities of organic synthesis.For the development of a new fluorescent molecular sensor consisting of a recognition moiety linked to a f...展开更多
The relationships between the phosphine content and various microbial populations,activities of different enzymes were investigated firstly.The results indicated that the phosphine content of samples from various envi...The relationships between the phosphine content and various microbial populations,activities of different enzymes were investigated firstly.The results indicated that the phosphine content of samples from various environments was positively related to total anaerobic microorganisms,organic phosphate compound-dissolving bacteria,denitrifying bacteria,and the activities of alkaline phosphatase and dehydrogenase,with correlation coefficients (R^2) up to 0.93,0.90,0.69,0.79,and 0.82,respectively.Results also sh...展开更多
The synthesis of two gold(I)complexes containing a pyridyl ligand with a polyethyleneglycol pendant arm at one position and a chromophore(aniline or coumarin)at the second coordination position is herein reported.Thes...The synthesis of two gold(I)complexes containing a pyridyl ligand with a polyethyleneglycol pendant arm at one position and a chromophore(aniline or coumarin)at the second coordination position is herein reported.These compounds have been observed to aggregate in acetonitrile/water mixtures and the results have been compared with two other gold(I)compounds previously synthesized by our group that contain a water soluble phosphane instead of the pyridyl ligand.We observed that the coumarin derivative is much more stable while the aniline analogue decomposes in the presence of small amounts of water.The aggregation of this coumarin gold(I)compound has been deeply studied by DLS,SAXS,optical microscopy and electron microscopy(SEM and cryo-TEM).The calculation of the crystal packing parameter confirms a vesicle-type assembly.In order to obtain more detailed information about the composition of vesicles,the number of molecules involved in the self-assembly process has been determined(Nagg=82).DFT calculations support these data,determining a size of around 90Åfor the vesicles,which may form coacervates to yield the larger structures observed under a microscope.展开更多
The demands for effective assembly of structurally complex molecular scaffolds from simple starting materials are continuously growing along with the development of organic chemistry.We have developed a tandem approac...The demands for effective assembly of structurally complex molecular scaffolds from simple starting materials are continuously growing along with the development of organic chemistry.We have developed a tandem approach that assembles simple 6-chloroethylphosphane,alkynyl imines(or alkynyl ketones),and nitrones into structurally complex isoxazolidine fused phospholene scaffolds through a sequential process involving phospha-Michael addition,intramolecular cyclization,and dearomatizing[3+2]cycloaddition reactions.The isoxazolidine-fused phospholene has three heteroatoms,including a junction phosphorus atom.After removing the coordinated tungsten group,these compounds can serve as potential P-stereogenic ligands and may have biological activities.Contrary to pyrroles and furans,the aromatic 2-phosphapyrroles and 2-phosphafurans are good 2r-electron candidates in the dearomative[3+2]cycloaddition reactions due to the poor overlap of the 2p-3p orbitals of the C=P moiety.展开更多
Comprehensive Summary This paper presents the first general examples of palladium-catalyzed desulfinative cross-coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts showing an inversion of the...Comprehensive Summary This paper presents the first general examples of palladium-catalyzed desulfinative cross-coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts showing an inversion of the conventional reactivity order of C-Br>C-Cl>C-OTf.The catalyst system,comprising of Pd(OAc)_(2)and tBuPhSelectPhos,exhibited excellent catalytic reactivity and chemoselectivity toward this reaction.This reaction had a wide range of substrate scopes and provided a simple and efficient method for the construction of functionalized biaryl motifs.Notably,the C-H···Pd interaction from the methine hydrogen of the C2-cyclohexyl group of the indolyl phosphine ligand with the Pd center may contribute a key factor in reactivity and chemoselectivity.Assisting with density functional theory(DFT)calculations,the results revealed that the oxidative addition step in this reaction was a controlling-chemoselectivity step.展开更多
文摘The geometry and the energy of conformers of PnHn+2(n=2-9) have been studied with PM3 method. It is concluded that gauche interaction between adjacent lone electron pairs and gauche interaction between P-H bond with adjacent P-P bond are important for predicting the stable conformer of open-chain phosphoanes.
基金Agencia Estatal de Investigación(PID2019-104379RB-C21,PID2022-136861NB-I00 and PID2020-117455GB-I00/AEI/10.13039/501100011033)Gobierno de Aragón(Research Group E07_23R)for financial support of our researchJ.C.Pérez-Sánchez also thanks the Spanish Ministerio de Universidades for a predoctoral grant(FPU21/01888).
文摘The coordination chemistry of chalcogenide ligands has always attracted significant interest in the field of inorganic chemistry,especially for soft metals such as those of group 11.Despite the scarcity of research on phosphane tellurides,we report on the synthesis and characterisation of five novel silver complexes containing the phosphane telluride ligand,TeP(iPr)_(3),along with other ancillary ligands such as mono or diphosphanes.Spectroscopic studies were performed to investigate the behaviour of these complexes,including their redox properties,as demonstrated by the 1,1′-diphenylphosphaneferrocene(dppf)silver derivatives.Additionally,these complexes showcase remarkable rapid interchange equilibrium,revealing silver species with distinctive Ag_(2)Te_(2) cores and a combination of bridging and terminal TeP(iPr)_(3) ligands.A promising avenue for further investigation and potential applications emerges.
文摘1 Results Over the past few years significant research has been directed toward the development of organic materials for potential application in molecular photonic devices[1] and the development of sensors[2].Interest in these materials is primarily due to the infinite numbers of possible molecular structures with the desired properties,by virtue of the tremendous capabilities of organic synthesis.For the development of a new fluorescent molecular sensor consisting of a recognition moiety linked to a f...
文摘The relationships between the phosphine content and various microbial populations,activities of different enzymes were investigated firstly.The results indicated that the phosphine content of samples from various environments was positively related to total anaerobic microorganisms,organic phosphate compound-dissolving bacteria,denitrifying bacteria,and the activities of alkaline phosphatase and dehydrogenase,with correlation coefficients (R^2) up to 0.93,0.90,0.69,0.79,and 0.82,respectively.Results also sh...
基金grateful to the Ministerio de Ciencia e Innovación of Spain(Projects PID2019-104121GB-I00 and PID2020-115637GB-I00)This work was supported by the Associate Laboratory for Green Chemistry-LAQV,which is financed by national funds from FCT/MCTES(UID/QUI/50006/2019)+2 种基金The authors would also like to acknowledge the International Research Network Hetero-elements and Coordination Chemistry:from Concepts to Applications(HC3A)and Spanish Network Materiales Supramoleculares Funcionales(RED2018-102331-T)This article is based on work from COST Actions CA 17140“Cancer Nanomedicine from the Bench to the Bedside”and CA18202-NECTAR supported by COST(European Cooperation in Science and Technology)SAXS experiments were performed at the NCD-BL11 beamline of the ALBA Synchrotron Light Facility in collaboration with the ALBA staff.
文摘The synthesis of two gold(I)complexes containing a pyridyl ligand with a polyethyleneglycol pendant arm at one position and a chromophore(aniline or coumarin)at the second coordination position is herein reported.These compounds have been observed to aggregate in acetonitrile/water mixtures and the results have been compared with two other gold(I)compounds previously synthesized by our group that contain a water soluble phosphane instead of the pyridyl ligand.We observed that the coumarin derivative is much more stable while the aniline analogue decomposes in the presence of small amounts of water.The aggregation of this coumarin gold(I)compound has been deeply studied by DLS,SAXS,optical microscopy and electron microscopy(SEM and cryo-TEM).The calculation of the crystal packing parameter confirms a vesicle-type assembly.In order to obtain more detailed information about the composition of vesicles,the number of molecules involved in the self-assembly process has been determined(Nagg=82).DFT calculations support these data,determining a size of around 90Åfor the vesicles,which may form coacervates to yield the larger structures observed under a microscope.
基金support from the National Natural Science Foundation of China(22171245).
文摘The demands for effective assembly of structurally complex molecular scaffolds from simple starting materials are continuously growing along with the development of organic chemistry.We have developed a tandem approach that assembles simple 6-chloroethylphosphane,alkynyl imines(or alkynyl ketones),and nitrones into structurally complex isoxazolidine fused phospholene scaffolds through a sequential process involving phospha-Michael addition,intramolecular cyclization,and dearomatizing[3+2]cycloaddition reactions.The isoxazolidine-fused phospholene has three heteroatoms,including a junction phosphorus atom.After removing the coordinated tungsten group,these compounds can serve as potential P-stereogenic ligands and may have biological activities.Contrary to pyrroles and furans,the aromatic 2-phosphapyrroles and 2-phosphafurans are good 2r-electron candidates in the dearomative[3+2]cycloaddition reactions due to the poor overlap of the 2p-3p orbitals of the C=P moiety.
基金the Research Grants Council of the Hong Kong Special Administrative Region,China(PolyU 15302821,15300220,and 25301819)the National Natural Science Foundation of China(21972122)for their financial support.
文摘Comprehensive Summary This paper presents the first general examples of palladium-catalyzed desulfinative cross-coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts showing an inversion of the conventional reactivity order of C-Br>C-Cl>C-OTf.The catalyst system,comprising of Pd(OAc)_(2)and tBuPhSelectPhos,exhibited excellent catalytic reactivity and chemoselectivity toward this reaction.This reaction had a wide range of substrate scopes and provided a simple and efficient method for the construction of functionalized biaryl motifs.Notably,the C-H···Pd interaction from the methine hydrogen of the C2-cyclohexyl group of the indolyl phosphine ligand with the Pd center may contribute a key factor in reactivity and chemoselectivity.Assisting with density functional theory(DFT)calculations,the results revealed that the oxidative addition step in this reaction was a controlling-chemoselectivity step.
