The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1...The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H/13C--NMR. Theproposal concerning mechanism was discussed herewith and the structure was reportedas well. Crystallographic data: Mr= 563. 85, monoclinicl P21/n(# 14); a= 8. 009(2), b= 17. 600(5), c=12. 003(4) A; β=95. 91(2)°; V= 1683. 0 (9) A3; Z=4;Dc=2. 22 g. cm-3; F(000) = 1048, μ=89. 27 cm-1 ; final R=0. 039 and Rw=0. 049for 2121 observable reflections with (I≥3. cσ(I) ). The crystal structure determinationshows that S atom coordinates to all three metal (W,Fe,Co) atoms in a μ3,-fashion,thetitle cluster core has the tetrahedral skeleton.展开更多
Competition at metal-ligand interfaces has long been recognized as a pivotal process in constructing multiscale nanostructures,wherein there is a delicate balance of coordination that yields novel structures and prope...Competition at metal-ligand interfaces has long been recognized as a pivotal process in constructing multiscale nanostructures,wherein there is a delicate balance of coordination that yields novel structures and properties.However,elucidating the underlying mechanisms and establishing design principles remain challenging.Here,we strategically introduce competition between Au(I)-thiolates and Na2S(inorganic sulfur),leading to the synthesis of an organic-inorganic hybrid-sulfur-containing cluster[Au_(22)(SR)_(17)S_(3)]−(SR=thiolate).X-ray absorption spectroscopy and tandem mass spectrometry revealed its structural features,where the gold sulfido cores(inorganic sulfide)were protected by gold-thiolates(organosulfur).More importantly,real-time electrospray ionization-mass spectrometry elucidated its formation process as a three-stage mechanism involving seed incubation,associative growth,and size-focusing.Through the extension of this approach,the nuclearity of gold sulfido clusters became tunable(e.g.,[Au_(22)(SR)_(14)S_(5)]^(2−)).This work not only introduces a novel category of atomically precise gold nanomaterials with appealing highlyemissive properties but also provides insights into the design of coordination competition for precise composition engineering of metal nanomaterials.展开更多
Title compound,Mr=1273.16,was synthesized by a substitution reaction and its crystal' is triclinic belonging to space group P1 with cell parameters:a=13.944(2),b=14.143(7),c=14.233(3), A,a=77.35(3)°,β=69.94(...Title compound,Mr=1273.16,was synthesized by a substitution reaction and its crystal' is triclinic belonging to space group P1 with cell parameters:a=13.944(2),b=14.143(7),c=14.233(3), A,a=77.35(3)°,β=69.94(2)°,γ=63.50(3)°,V=2351(1)A^3,Z=2,D_c=1.799g cm^(-3).Room tem- perature,graphite-filtered Mo K_α,radiation(λ=0.71073A)was used for data collection.μ=14.988 cm^(-1),F(000)=1280,R=0.051 for 7025 observed reflections.The crystal consists of decrete cluster molecules containing a duster core[Mo_3(μ_3-S)]^(10+)with three μ-S,one μ-dtp(dtp=[S_2P(OC_2H_5)]^(2-), three x-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom.The bónds of cluster skeleton[Mo_3(μ_3-S)(μ-S)_3]^(4+),Mo—Mo 2.744～2.766,Mo—(μ_3-S)2.340～2.342 and Mo—(μ-S)2.272～2.296 A,are comparable with those found in the related analogues.展开更多
The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe)...The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.展开更多
文摘The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H/13C--NMR. Theproposal concerning mechanism was discussed herewith and the structure was reportedas well. Crystallographic data: Mr= 563. 85, monoclinicl P21/n(# 14); a= 8. 009(2), b= 17. 600(5), c=12. 003(4) A; β=95. 91(2)°; V= 1683. 0 (9) A3; Z=4;Dc=2. 22 g. cm-3; F(000) = 1048, μ=89. 27 cm-1 ; final R=0. 039 and Rw=0. 049for 2121 observable reflections with (I≥3. cσ(I) ). The crystal structure determinationshows that S atom coordinates to all three metal (W,Fe,Co) atoms in a μ3,-fashion,thetitle cluster core has the tetrahedral skeleton.
基金supported by the National Natural Science Foundation of China(grant no.22071174)support from the Ministry of Education,Singapore,Academic Research Fund(AcRF)grant no.A-8000054-01-00.T.Chen acknowledges the University Development Fund,Research Start-up Fund(grant no.UDF01002910)+1 种基金support from the Natural Sciences and Engineering Research Council(NSERC),CanadaThis research used resources of the Advanced Photon Source,an Office of Science User Facility operated for the US Department of Energy(DOE)Office of Science by Argonne National Laboratory and was supported by the US DOE under contract no.DE-AC02-06CH11357 and the Canadian Light Source(CLS)and its funding partners.
文摘Competition at metal-ligand interfaces has long been recognized as a pivotal process in constructing multiscale nanostructures,wherein there is a delicate balance of coordination that yields novel structures and properties.However,elucidating the underlying mechanisms and establishing design principles remain challenging.Here,we strategically introduce competition between Au(I)-thiolates and Na2S(inorganic sulfur),leading to the synthesis of an organic-inorganic hybrid-sulfur-containing cluster[Au_(22)(SR)_(17)S_(3)]−(SR=thiolate).X-ray absorption spectroscopy and tandem mass spectrometry revealed its structural features,where the gold sulfido cores(inorganic sulfide)were protected by gold-thiolates(organosulfur).More importantly,real-time electrospray ionization-mass spectrometry elucidated its formation process as a three-stage mechanism involving seed incubation,associative growth,and size-focusing.Through the extension of this approach,the nuclearity of gold sulfido clusters became tunable(e.g.,[Au_(22)(SR)_(14)S_(5)]^(2−)).This work not only introduces a novel category of atomically precise gold nanomaterials with appealing highlyemissive properties but also provides insights into the design of coordination competition for precise composition engineering of metal nanomaterials.
文摘Title compound,Mr=1273.16,was synthesized by a substitution reaction and its crystal' is triclinic belonging to space group P1 with cell parameters:a=13.944(2),b=14.143(7),c=14.233(3), A,a=77.35(3)°,β=69.94(2)°,γ=63.50(3)°,V=2351(1)A^3,Z=2,D_c=1.799g cm^(-3).Room tem- perature,graphite-filtered Mo K_α,radiation(λ=0.71073A)was used for data collection.μ=14.988 cm^(-1),F(000)=1280,R=0.051 for 7025 observed reflections.The crystal consists of decrete cluster molecules containing a duster core[Mo_3(μ_3-S)]^(10+)with three μ-S,one μ-dtp(dtp=[S_2P(OC_2H_5)]^(2-), three x-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom.The bónds of cluster skeleton[Mo_3(μ_3-S)(μ-S)_3]^(4+),Mo—Mo 2.744～2.766,Mo—(μ_3-S)2.340～2.342 and Mo—(μ-S)2.272～2.296 A,are comparable with those found in the related analogues.
文摘The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.
