Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural anal...Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (I) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the CuACu separation of 6.231 A. The copper (I) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P 1 with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3) A, α = 98.289(1), β = 91.232(1), γ = 106.496(1)°, V = 4117.60(9) A3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr= 1659.37, Dc= 1.338 g/cm3, F(000) = 1708, μ = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I>2σ(I).展开更多
Self-assembly between the building blocks of Pd(Et2dtc)2 (Et2dtc = diethyldithio- carbamate) and [Cu2(m-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) gave a new heterotetranuclear complex [Cu2Pd2(m-dppm)2(m-...Self-assembly between the building blocks of Pd(Et2dtc)2 (Et2dtc = diethyldithio- carbamate) and [Cu2(m-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) gave a new heterotetranuclear complex [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3-Et2dtc)2](ClO4)2H2O (C70H86Cl2Cu2- N4O9P4Pd2S8, Mr = 1932.56), and its crystal structure has been determined by X-ray crystallo- graphy. It crystallizes in triclinic, space group P with a = 11.9834(6), b = 12.5624(6), c = 14.5603(8) ? a = 101.393 (1), b = 103.300 (1), g = 96.310(1), V = 2063.2(2) 3, Z = 1, Dc = 1.544 g/cm3, m(MoKa) = 1336 cm-1 and F(000) = 978. The total and unique reflections are 8710 and 5400, respectively. The structure was refined to R = 0.0860 and wR = 0.1996 for 3914 observed reflections with I > 2s(I). The title complex consists of the cation [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3- Et2dtc)2]2+, anion ClO4- and solvate H2O. The Pd(Ⅱ) atoms are located at the approximately square-planar environments with PS3 donors and the Cu(I) atoms display distorted tetrahedral geometries.展开更多
The title complex Cd(dppf)Br2 (dppf=1,1′-bis(diphenylphosphino)ferrocene) (C34H28Br2 P2CdFe, Mr=826.57) has been synthesized and characterized by X-ray diffraction. The crystal is in monoclinic, space group C2/c with...The title complex Cd(dppf)Br2 (dppf=1,1′-bis(diphenylphosphino)ferrocene) (C34H28Br2 P2CdFe, Mr=826.57) has been synthesized and characterized by X-ray diffraction. The crystal is in monoclinic, space group C2/c with cell parameters: a = 34.285(4), b = 10.050(1), c = 18.697(2) ? β= 98.843(3)? V = 6366(1)3, Z = 8, Dc = 1.725g/cm3, (MoKa) = 0.71073 ? =3.757mm-1, F(000)=3248. The final refinement with 4469 observed reflections and 361 parameters gave R=0.0584 and wR=0.1522. The 1,1′-bis(diphenylphosphino)ferrocene group is connected to the Cd atom as a bidentate ligand. The Cd atom has a distorted tetrahedral coordination.展开更多
The tetranuclear complex[Ag4(μ-Ph2PNHPPh2)2(μ-OPh2PNPPh2O)2] (PF6)2·CH3COCH3 containing bis(diphenylphosphino)amine (Ph2PNHPPh2) and deprotonated bis- (diphenylphosphino)amine-dioxide (OPh2PNPPh2O...The tetranuclear complex[Ag4(μ-Ph2PNHPPh2)2(μ-OPh2PNPPh2O)2] (PF6)2·CH3COCH3 containing bis(diphenylphosphino)amine (Ph2PNHPPh2) and deprotonated bis- (diphenylphosphino)amine-dioxide (OPh2PNPPh2O) was isolated and characterized by X-ray crystallography. The deprotonated OPh2PNPPh2O acts as a tridentate ligand in a chelating and bridging mode. Two of the four Ag atoms are in a trigonal planar environment composed of PO2 chromophore, whereas the other two are coordinated with PN donors in a distorted linear arrangement. The title complex (C51H47Ag2F6N2O3P5) crystallizes in triclinic, space group P1^- with a = 12.9552 (2), b = 14.1691(3), c = 15.8110(3)A°, α = 68.7500(10), β= 86.8840(10), γ = 75.6170(10)°, V= 2618.16 (8) A°^3, Mr= 1220.50, Z = 2, Dc= 1.548 g/cm^3, F(000) = 1228 and μ(MoKα) = 0.965 mm^-1. The final refinements converged at R = 0.0679 and wR = 0.1528 for 7001 observed reflections (I〉 2σ(I)).展开更多
The binuclear complex [Ag2(m-Ph2PNHPPh2)3](ClO4)2CH2Cl2CH3OH (Ph2PNHP- Ph2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis- (diphenylphosphino)amine in equimolar ratio through self-ass...The binuclear complex [Ag2(m-Ph2PNHPPh2)3](ClO4)2CH2Cl2CH3OH (Ph2PNHP- Ph2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis- (diphenylphosphino)amine in equimolar ratio through self-assembly. The coordination cation affords a triply-bridging [Ag2L3]-type coordination moiety. The silver atom is in a trigonal planar environment with P3 coordination chromophore. The complex (C74H69Cl4N3O9P6Ag2) crystallizes in monoclinic, space group Cc with a = 18.3738(1), b = 20.0207(4), c = 20.5422(4) ? b = 95.829(1), V = 7517.5(2) 3, Z = 4, Mr = 1687.68, Dc = 1.491 g/cm3, F(000) = 3432, m = 0.848 mm-1, the final R = 0.0460 and wR = 0.0935 for 7005 observed reflections with I > 2s(I).展开更多
A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency (TOF) of 1190 h^-1 at 100% sele...A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency (TOF) of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.展开更多
The reaction between [Cu2(m-dppm)2(MeCN)4](ClO4)2(dppm = bis(diphenylphos- phino)methane) and [Zn(PhS)2(bpy)] (bpy = 2,2-bipyridine, PhS = benzenethiolate) gave the complex [Cu2(m-dppm)2(m-PhS)(MeCN)]ClO40.5(Et2O)(C58...The reaction between [Cu2(m-dppm)2(MeCN)4](ClO4)2(dppm = bis(diphenylphos- phino)methane) and [Zn(PhS)2(bpy)] (bpy = 2,2-bipyridine, PhS = benzenethiolate) gave the complex [Cu2(m-dppm)2(m-PhS)(MeCN)]ClO40.5(Et2O)(C58H52ClNO4P4SCu20.5Et2O) which was determined by X-ray single-crystal diffraction. The crystal is of orthorhombic, space group P212121 with a = 13.6157(3), b = 20.8022(6), c = 21.3299(6) ? V = 6041.4(3) 3, Mr = 1182.54, Dc = 1.300 g/cm3, F(000) = 2444, m = 0.934 mm-1 and Z = 4. The final R = 0.0773 and wR = 0.1843 for 7744 observed reflections (I > 2s(I)). The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate. One copper atom is in a distorted trigonal bipyramidal environ- ment, whereas the other adopts a distorted tetrahedral geometry.展开更多
基金This work was supported by NNSFC(No.20171044and2023074) the project for "Hundred Talents" from the Chinese Academy of Sciences
文摘Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (I) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the CuACu separation of 6.231 A. The copper (I) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P 1 with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3) A, α = 98.289(1), β = 91.232(1), γ = 106.496(1)°, V = 4117.60(9) A3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr= 1659.37, Dc= 1.338 g/cm3, F(000) = 1708, μ = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I>2σ(I).
基金Science Foundation and the Government of Guangdong province
文摘Self-assembly between the building blocks of Pd(Et2dtc)2 (Et2dtc = diethyldithio- carbamate) and [Cu2(m-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) gave a new heterotetranuclear complex [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3-Et2dtc)2](ClO4)2H2O (C70H86Cl2Cu2- N4O9P4Pd2S8, Mr = 1932.56), and its crystal structure has been determined by X-ray crystallo- graphy. It crystallizes in triclinic, space group P with a = 11.9834(6), b = 12.5624(6), c = 14.5603(8) ? a = 101.393 (1), b = 103.300 (1), g = 96.310(1), V = 2063.2(2) 3, Z = 1, Dc = 1.544 g/cm3, m(MoKa) = 1336 cm-1 and F(000) = 978. The total and unique reflections are 8710 and 5400, respectively. The structure was refined to R = 0.0860 and wR = 0.1996 for 3914 observed reflections with I > 2s(I). The title complex consists of the cation [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3- Et2dtc)2]2+, anion ClO4- and solvate H2O. The Pd(Ⅱ) atoms are located at the approximately square-planar environments with PS3 donors and the Cu(I) atoms display distorted tetrahedral geometries.
基金the provincial education foundation of Fujian (JA99135) the test foundation of Fuzhou University
文摘The title complex Cd(dppf)Br2 (dppf=1,1′-bis(diphenylphosphino)ferrocene) (C34H28Br2 P2CdFe, Mr=826.57) has been synthesized and characterized by X-ray diffraction. The crystal is in monoclinic, space group C2/c with cell parameters: a = 34.285(4), b = 10.050(1), c = 18.697(2) ? β= 98.843(3)? V = 6366(1)3, Z = 8, Dc = 1.725g/cm3, (MoKa) = 0.71073 ? =3.757mm-1, F(000)=3248. The final refinement with 4469 observed reflections and 361 parameters gave R=0.0584 and wR=0.1522. The 1,1′-bis(diphenylphosphino)ferrocene group is connected to the Cd atom as a bidentate ligand. The Cd atom has a distorted tetrahedral coordination.
基金This work was supported by NSF of Fujian Province (E0310029 and E0420002)
文摘The tetranuclear complex[Ag4(μ-Ph2PNHPPh2)2(μ-OPh2PNPPh2O)2] (PF6)2·CH3COCH3 containing bis(diphenylphosphino)amine (Ph2PNHPPh2) and deprotonated bis- (diphenylphosphino)amine-dioxide (OPh2PNPPh2O) was isolated and characterized by X-ray crystallography. The deprotonated OPh2PNPPh2O acts as a tridentate ligand in a chelating and bridging mode. Two of the four Ag atoms are in a trigonal planar environment composed of PO2 chromophore, whereas the other two are coordinated with PN donors in a distorted linear arrangement. The title complex (C51H47Ag2F6N2O3P5) crystallizes in triclinic, space group P1^- with a = 12.9552 (2), b = 14.1691(3), c = 15.8110(3)A°, α = 68.7500(10), β= 86.8840(10), γ = 75.6170(10)°, V= 2618.16 (8) A°^3, Mr= 1220.50, Z = 2, Dc= 1.548 g/cm^3, F(000) = 1228 and μ(MoKα) = 0.965 mm^-1. The final refinements converged at R = 0.0679 and wR = 0.1528 for 7001 observed reflections (I〉 2σ(I)).
基金This work was supported by NNSFC (No. 20171044) and the project for "undred Talents from" the Chinese Academy of Sciences
文摘The binuclear complex [Ag2(m-Ph2PNHPPh2)3](ClO4)2CH2Cl2CH3OH (Ph2PNHP- Ph2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis- (diphenylphosphino)amine in equimolar ratio through self-assembly. The coordination cation affords a triply-bridging [Ag2L3]-type coordination moiety. The silver atom is in a trigonal planar environment with P3 coordination chromophore. The complex (C74H69Cl4N3O9P6Ag2) crystallizes in monoclinic, space group Cc with a = 18.3738(1), b = 20.0207(4), c = 20.5422(4) ? b = 95.829(1), V = 7517.5(2) 3, Z = 4, Mr = 1687.68, Dc = 1.491 g/cm3, F(000) = 3432, m = 0.848 mm-1, the final R = 0.0460 and wR = 0.0935 for 7005 observed reflections with I > 2s(I).
基金the National Natural Science Foundation of China (No.20173048) the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20030335068)+1 种基金 the Scientific Research Fund of Zhcjiang Provincial Education Department (No. 20040320) Zhcjiang Provincial Natural Science Foundation of China (No. Y405088).
文摘A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency (TOF) of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.
文摘The reaction between [Cu2(m-dppm)2(MeCN)4](ClO4)2(dppm = bis(diphenylphos- phino)methane) and [Zn(PhS)2(bpy)] (bpy = 2,2-bipyridine, PhS = benzenethiolate) gave the complex [Cu2(m-dppm)2(m-PhS)(MeCN)]ClO40.5(Et2O)(C58H52ClNO4P4SCu20.5Et2O) which was determined by X-ray single-crystal diffraction. The crystal is of orthorhombic, space group P212121 with a = 13.6157(3), b = 20.8022(6), c = 21.3299(6) ? V = 6041.4(3) 3, Mr = 1182.54, Dc = 1.300 g/cm3, F(000) = 2444, m = 0.934 mm-1 and Z = 4. The final R = 0.0773 and wR = 0.1843 for 7744 observed reflections (I > 2s(I)). The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate. One copper atom is in a distorted trigonal bipyramidal environ- ment, whereas the other adopts a distorted tetrahedral geometry.