The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-h...The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-half functional （BHandHLYP and BHandH） methods have been applied in the geometry optimization, and BHandH method at the 6-31G^＊ level （Pd, 3-21G^＊） can give adequate accuracy for both free sulfoxides and their Pd （Ⅱ） complexes. As compared to diphenyl sulfoxide （DPSO）, the better affinity of di-n-hexyl sulfoxide （DHSO） towards Pd（Ⅱ） has been reasonably explained by a stronger electronic transfer, shorter Pd-S bond length and a larger binding energy in its Pd （Ⅱ） complex.展开更多
The title compound bis（1-（4-（dimethylamino）benzylidene）-4-phenylthiosemicar-bazato）-palladium（Ⅱ）（PdL2） was obtained by reacting 1-（4-（dimethylamino）benzylidene）-4-phenyl-thiosemicarbazide with dichloro...The title compound bis（1-（4-（dimethylamino）benzylidene）-4-phenylthiosemicar-bazato）-palladium（Ⅱ）（PdL2） was obtained by reacting 1-（4-（dimethylamino）benzylidene）-4-phenyl-thiosemicarbazide with dichlorobis（benzonitrile）palladium（Ⅱ） in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide（DMF） solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485（15）,b = 7.090（5）,c = 17.595（11） ,β = 121.21（3）o,V = 1972（2） 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F（000） = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd（Ⅱ） perturbed ligand π-π＊ transition and metal-to-ligand charge transfer（MLCT） transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π＊（IL） state and MLCT state dual fluorescent emissions in organic solvent at room temperature.展开更多
The structure of trans-[Pd(dtco-3-OH)2] (ClO4)2·2DMSO, in which dtco-3-OH is dithiacyclooctan-3-ol and DMSO is dimethyl sulfoxide, was determined by X-ray crystallographic analysis. The crystal data: space group ...The structure of trans-[Pd(dtco-3-OH)2] (ClO4)2·2DMSO, in which dtco-3-OH is dithiacyclooctan-3-ol and DMSO is dimethyl sulfoxide, was determined by X-ray crystallographic analysis. The crystal data: space group pi, a = 0.7077(2) nm, b = 1.0788(1) nm, c = 1.1111(1) nm, α=67.710(8)°, β = 73. 59(2)°, γ = 85. 39(2)°,R1 = 0 . 0368 and Rw = 0.0998. The palladium (II) is coordinated by four sulfur atoms with a regular square planar configuration. The Pd-S distances are 0.2314(1) and 0.2317(1) nm, respectively. Both dtco-3-OH ligands are in the boat-chair configuration and two hydroxyl groups are on the opposite sites of the PdS4 coordination plane and are towards Pd(II). The Pd-O distance is 0. 285 nm, indicating a weak interaction between them. A typical hydrogen bond between the hydroxyl group of dtco-3-OH ligand and DMSO was observed in the crystal structure. An aqueous solution prepared with the crystals of the complex was used for the investigation of electrospray mass spectrometry ( ESMS ). Besides trans -[ Pd ( dtco-3-OH)2]2+. 2DMSO observed, in the full scan spectrum of ESMS, all relative species of it, which were probably produced during electrospray ionization process, were also detected. From these experiments, it reveals that ESMS is a powerful tool for studying noncovalent interaction present in solution between inorganic complexes and solvents.展开更多
A palladium(Ⅱ) complex, PdLCl2·PdCl4, L=4-bromo-2,6-bis(N,N-diethylaminomethylene)pyridine, was synthesized and its crystal structure was determined by X-ray analysis. The complex crystallizes in monoclinic syst...A palladium(Ⅱ) complex, PdLCl2·PdCl4, L=4-bromo-2,6-bis(N,N-diethylaminomethylene)pyridine, was synthesized and its crystal structure was determined by X-ray analysis. The complex crystallizes in monoclinic system with space group Cc, a=0.845 1(17) nm, b=1.836 5(4) nm, c=2.715 8(5) nm, β=93.99(3)°, V=4.204 8(15) nm3, Z=4, R1=0.037 7 and wR2=0.076 9. The coordination geometry of the Pd atom in the cation is a slightly distorted square planar, with one pyridyl N and two N atoms of the diethylamine ligand, together with one Cl atom. The dihedral angle between the square planar (N3PdCl) and the pyridyl ring is 10.3(4)°. CCDC: 623421.展开更多
A novel palladium(Ⅱ) complex [Pd(Phen)(TsserNO)]·H2O (Phen=1,10-phenanthroline; TsserNO=4- toluenesulfonyl-L-serinate dianion) has been prepared and structurally characterized, the cytotoxicity in vitro has also...A novel palladium(Ⅱ) complex [Pd(Phen)(TsserNO)]·H2O (Phen=1,10-phenanthroline; TsserNO=4- toluenesulfonyl-L-serinate dianion) has been prepared and structurally characterized, the cytotoxicity in vitro has also been investigated by MTT and SRB assays. The complex crystallizes in the monoclinic system, space group P21 with cell parameters a=0.618 64(14) nm, b=1.768 9(4) nm, c=0.990 2(2) nm, β=102.392(4)°, V=1.058 3(4) nm3 and Z=2. The complex had selectivity against HL-60, BGC-823, Bel-7402 and KB cells lines, its cytotoxicity is equal to that of cisplatin against BGC-823 and Bel-7402 cells lines, however it is less potent than cisplatin against HL-60 and KB cell lines.<Keywords>antitumor; palladium(Ⅱ) complex; crystal展开更多
Six palladium? complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R IEAI)2, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p CH3C6H4 IEAI)2 (2) cry stallizes...Six palladium? complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R IEAI)2, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p CH3C6H4 IEAI)2 (2) cry stallizes in the monoclinic system, space group P21/c,with a=1.2002(2),b=0.9972(2),c=1.1121(2)nm,β=90.43(3)°,Z=2,F(000)=616,μ=7.44cm-1. The final R and wR are 0.0244 and 0.0625 for 2620 observed reflections with I ≥ 2σ(I), respectively. The geometry around the Pd? ions in those complexes has a distorted PdN4 square plane, the Schiff base ligands R IEAI- being coordinated through their oximino nitrogen atoms and imino nitrogen atoms.展开更多
基金This work was supported by the NNSFC (20332030, 20572027), Research Grants Council of Hong Kong and SRF for ROCS, State Education Ministry
文摘The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-half functional （BHandHLYP and BHandH） methods have been applied in the geometry optimization, and BHandH method at the 6-31G^＊ level （Pd, 3-21G^＊） can give adequate accuracy for both free sulfoxides and their Pd （Ⅱ） complexes. As compared to diphenyl sulfoxide （DPSO）, the better affinity of di-n-hexyl sulfoxide （DHSO） towards Pd（Ⅱ） has been reasonably explained by a stronger electronic transfer, shorter Pd-S bond length and a larger binding energy in its Pd （Ⅱ） complex.
基金supported by the National Basic Research Program of China (973 Program,2007CB815301)NSF (No. 20721001)the Science & Technology Innovation Project of Xiamen University (No. K70025)
文摘The title compound bis（1-（4-（dimethylamino）benzylidene）-4-phenylthiosemicar-bazato）-palladium（Ⅱ）（PdL2） was obtained by reacting 1-（4-（dimethylamino）benzylidene）-4-phenyl-thiosemicarbazide with dichlorobis（benzonitrile）palladium（Ⅱ） in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide（DMF） solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485（15）,b = 7.090（5）,c = 17.595（11） ,β = 121.21（3）o,V = 1972（2） 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F（000） = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd（Ⅱ） perturbed ligand π-π＊ transition and metal-to-ligand charge transfer（MLCT） transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π＊（IL） state and MLCT state dual fluorescent emissions in organic solvent at room temperature.
基金Project supported by the National Natural Science Foundation of China (Nos. 29871017, 29823001) and the Natural Science Foundation of Jiangsu Province (No. BK97015).
文摘The structure of trans-[Pd(dtco-3-OH)2] (ClO4)2·2DMSO, in which dtco-3-OH is dithiacyclooctan-3-ol and DMSO is dimethyl sulfoxide, was determined by X-ray crystallographic analysis. The crystal data: space group pi, a = 0.7077(2) nm, b = 1.0788(1) nm, c = 1.1111(1) nm, α=67.710(8)°, β = 73. 59(2)°, γ = 85. 39(2)°,R1 = 0 . 0368 and Rw = 0.0998. The palladium (II) is coordinated by four sulfur atoms with a regular square planar configuration. The Pd-S distances are 0.2314(1) and 0.2317(1) nm, respectively. Both dtco-3-OH ligands are in the boat-chair configuration and two hydroxyl groups are on the opposite sites of the PdS4 coordination plane and are towards Pd(II). The Pd-O distance is 0. 285 nm, indicating a weak interaction between them. A typical hydrogen bond between the hydroxyl group of dtco-3-OH ligand and DMSO was observed in the crystal structure. An aqueous solution prepared with the crystals of the complex was used for the investigation of electrospray mass spectrometry ( ESMS ). Besides trans -[ Pd ( dtco-3-OH)2]2+. 2DMSO observed, in the full scan spectrum of ESMS, all relative species of it, which were probably produced during electrospray ionization process, were also detected. From these experiments, it reveals that ESMS is a powerful tool for studying noncovalent interaction present in solution between inorganic complexes and solvents.
文摘A palladium(Ⅱ) complex, PdLCl2·PdCl4, L=4-bromo-2,6-bis(N,N-diethylaminomethylene)pyridine, was synthesized and its crystal structure was determined by X-ray analysis. The complex crystallizes in monoclinic system with space group Cc, a=0.845 1(17) nm, b=1.836 5(4) nm, c=2.715 8(5) nm, β=93.99(3)°, V=4.204 8(15) nm3, Z=4, R1=0.037 7 and wR2=0.076 9. The coordination geometry of the Pd atom in the cation is a slightly distorted square planar, with one pyridyl N and two N atoms of the diethylamine ligand, together with one Cl atom. The dihedral angle between the square planar (N3PdCl) and the pyridyl ring is 10.3(4)°. CCDC: 623421.
文摘A novel palladium(Ⅱ) complex [Pd(Phen)(TsserNO)]·H2O (Phen=1,10-phenanthroline; TsserNO=4- toluenesulfonyl-L-serinate dianion) has been prepared and structurally characterized, the cytotoxicity in vitro has also been investigated by MTT and SRB assays. The complex crystallizes in the monoclinic system, space group P21 with cell parameters a=0.618 64(14) nm, b=1.768 9(4) nm, c=0.990 2(2) nm, β=102.392(4)°, V=1.058 3(4) nm3 and Z=2. The complex had selectivity against HL-60, BGC-823, Bel-7402 and KB cells lines, its cytotoxicity is equal to that of cisplatin against BGC-823 and Bel-7402 cells lines, however it is less potent than cisplatin against HL-60 and KB cell lines.<Keywords>antitumor; palladium(Ⅱ) complex; crystal
文摘Six palladium? complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R IEAI)2, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p CH3C6H4 IEAI)2 (2) cry stallizes in the monoclinic system, space group P21/c,with a=1.2002(2),b=0.9972(2),c=1.1121(2)nm,β=90.43(3)°,Z=2,F(000)=616,μ=7.44cm-1. The final R and wR are 0.0244 and 0.0625 for 2620 observed reflections with I ≥ 2σ(I), respectively. The geometry around the Pd? ions in those complexes has a distorted PdN4 square plane, the Schiff base ligands R IEAI- being coordinated through their oximino nitrogen atoms and imino nitrogen atoms.
