The title compound N,N,N’,N’-tetra[(diphenylphosphine)methyl]-1,4-phenylenediamine is synthesized by reaction of [Ph2P(CH2OH)2]Cl and 1,4-phenylenediamine.It is characterized by elemental analysis,IR,31PNMR,1HNMR.Si...The title compound N,N,N’,N’-tetra[(diphenylphosphine)methyl]-1,4-phenylenediamine is synthesized by reaction of [Ph2P(CH2OH)2]Cl and 1,4-phenylenediamine.It is characterized by elemental analysis,IR,31PNMR,1HNMR.Single crystal X-ray diffraction analysis reveals that it is centro-symmetric with the inversion center at the centroid of phenylene.Intermolecular π–π stacking interactions between phenyl rings make molecules arrange along the b axis into one-dimensional chains,while these chains are further extended by intermolecular C-H…π interactions into three-dimensional supramolecular structure.The crystal is orthorhombic system with space group Pbca,Mr: 900.90,a=12.215(1),b=14.460(2),c=27.821(3),β=90°,v=4914.0(9)3,z=4,Dc=1.218 mg·m-3,F(000)=1896,R=0.0487,wR=0.1245.展开更多
The proton dissociation constants of some novel water soluble phosphine ligands containing phosphonic acid were determined pH metrically at 25℃ and at an inonic strength of 0.1mol·L -1 (KNO 3).From these data it...The proton dissociation constants of some novel water soluble phosphine ligands containing phosphonic acid were determined pH metrically at 25℃ and at an inonic strength of 0.1mol·L -1 (KNO 3).From these data it had been established that when the complexing group PPh 2 was introdued,the proton dissociating power of phosphonic acid significantly increased and the p K 1,p K 2 values were 1.35～1.75 log units smaller than those of the corresponding 2 aminoethylphosphonic acid analogues;while ertheric linkenge was introdued into the corresponding phosphonic acid,the proton dissociating ability of NH + 3, PO 3H - groups decreased and that of PO 3H 2 group increased respectively;However,as hydroxyethyl group was introduced,all proton dissociating power of NH + 3, PO 3H - and PO 3H 2 groups decreased.The ultraviolet properties of this type of phosphine complexes were also determinated.展开更多
The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a ...The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a = 9.135(1), b = 9.772(1), c = 17.000(2) , a = 76.377(2), b = 78.333(2), g = 67.243(2)? Mr = 582.44, V = 1349.7(3) 3, Z = 2, Dc = 1.433 g/cm3, m(MoKa) = 0.581 mm-1 and F(000) = 596. A total of 5614 reflections were collected in the range of 2.30< q < 25.03? of which 4721 were independent (Rint = 0.0176) and 4159 observed reflections (I ≥ 2s(I)) were used in the refinement. R = 0.0326 and wR = 0.0867. The Mo centre is six-coordinated by four carbonyls (MoC 1.938(4), 2.003(4), 2.019(4), 2.035(4) ) and P, N atoms from the ligand (MoP 2.4812(8), MoN 2.349(3) ?. The coordination geometry of the complex can be described as an octahedron.展开更多
The title complex [Cu2(-dppm)2(-Et2dtc)](ClO4)EtOH0.25H2O (dppm = bis- (diphenylphosphino)methane, Et2dtc = diethyldithiocarbamate) has been synthesized and characterized by single-crystal X-ray diffraction analysis. ...The title complex [Cu2(-dppm)2(-Et2dtc)](ClO4)EtOH0.25H2O (dppm = bis- (diphenylphosphino)methane, Et2dtc = diethyldithiocarbamate) has been synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal structure is of monoclinic, space group C2/c with a = 42.587(1), b = 14.1653(4), c = 20.5649(5) ? = 105.945(1)? V =11928.6 3, C57H60.5ClCu2NO5.25P4S2, Mr = 1194.09, Z = 8, Dc = 1.330 g/cm3, (MoK) = 0.98 mm-1 and F(000) = 4948. A total of 15243 reflections were collected, of which 7322 were unique. The structure was refined to R = 0.0739 and wR = 0.1846 for 5135 observed reflections with I > 2(I). The crystal structure consists of the complex cation [Cu2(-dppm)2(-Et2dtc)]+, anion ClO4- and solvate H2O and EtOH, where the dinuclear Cu(Ⅰ) atoms are bridged doubly by two dppm ligands and singly by Et2dtc to give three five-membered rings. The Cu(Ⅰ) atom is in an approxi- mately trigonal-planar environment with the P2S chromophore. The short Cu贩稢u separation (2.7111 ? suggests the presence of metal-metal contact.展开更多
A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes...A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.展开更多
文摘The title compound N,N,N’,N’-tetra[(diphenylphosphine)methyl]-1,4-phenylenediamine is synthesized by reaction of [Ph2P(CH2OH)2]Cl and 1,4-phenylenediamine.It is characterized by elemental analysis,IR,31PNMR,1HNMR.Single crystal X-ray diffraction analysis reveals that it is centro-symmetric with the inversion center at the centroid of phenylene.Intermolecular π–π stacking interactions between phenyl rings make molecules arrange along the b axis into one-dimensional chains,while these chains are further extended by intermolecular C-H…π interactions into three-dimensional supramolecular structure.The crystal is orthorhombic system with space group Pbca,Mr: 900.90,a=12.215(1),b=14.460(2),c=27.821(3),β=90°,v=4914.0(9)3,z=4,Dc=1.218 mg·m-3,F(000)=1896,R=0.0487,wR=0.1245.
文摘The proton dissociation constants of some novel water soluble phosphine ligands containing phosphonic acid were determined pH metrically at 25℃ and at an inonic strength of 0.1mol·L -1 (KNO 3).From these data it had been established that when the complexing group PPh 2 was introdued,the proton dissociating power of phosphonic acid significantly increased and the p K 1,p K 2 values were 1.35～1.75 log units smaller than those of the corresponding 2 aminoethylphosphonic acid analogues;while ertheric linkenge was introdued into the corresponding phosphonic acid,the proton dissociating ability of NH + 3, PO 3H - groups decreased and that of PO 3H 2 group increased respectively;However,as hydroxyethyl group was introduced,all proton dissociating power of NH + 3, PO 3H - and PO 3H 2 groups decreased.The ultraviolet properties of this type of phosphine complexes were also determinated.
基金This work was supported by the National Natural Science Foundation of China (No. 20102003)
文摘The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a = 9.135(1), b = 9.772(1), c = 17.000(2) , a = 76.377(2), b = 78.333(2), g = 67.243(2)? Mr = 582.44, V = 1349.7(3) 3, Z = 2, Dc = 1.433 g/cm3, m(MoKa) = 0.581 mm-1 and F(000) = 596. A total of 5614 reflections were collected in the range of 2.30< q < 25.03? of which 4721 were independent (Rint = 0.0176) and 4159 observed reflections (I ≥ 2s(I)) were used in the refinement. R = 0.0326 and wR = 0.0867. The Mo centre is six-coordinated by four carbonyls (MoC 1.938(4), 2.003(4), 2.019(4), 2.035(4) ) and P, N atoms from the ligand (MoP 2.4812(8), MoN 2.349(3) ?. The coordination geometry of the complex can be described as an octahedron.
基金Supported by the Government of Guangdong province
文摘The title complex [Cu2(-dppm)2(-Et2dtc)](ClO4)EtOH0.25H2O (dppm = bis- (diphenylphosphino)methane, Et2dtc = diethyldithiocarbamate) has been synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal structure is of monoclinic, space group C2/c with a = 42.587(1), b = 14.1653(4), c = 20.5649(5) ? = 105.945(1)? V =11928.6 3, C57H60.5ClCu2NO5.25P4S2, Mr = 1194.09, Z = 8, Dc = 1.330 g/cm3, (MoK) = 0.98 mm-1 and F(000) = 4948. A total of 15243 reflections were collected, of which 7322 were unique. The structure was refined to R = 0.0739 and wR = 0.1846 for 5135 observed reflections with I > 2(I). The crystal structure consists of the complex cation [Cu2(-dppm)2(-Et2dtc)]+, anion ClO4- and solvate H2O and EtOH, where the dinuclear Cu(Ⅰ) atoms are bridged doubly by two dppm ligands and singly by Et2dtc to give three five-membered rings. The Cu(Ⅰ) atom is in an approxi- mately trigonal-planar environment with the P2S chromophore. The short Cu贩稢u separation (2.7111 ? suggests the presence of metal-metal contact.
文摘A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.
