A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2...A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2 5729(4) nm, b =1 4318(1) nm, c =2 1217(4) nm, β =111 56(1)°, V =6 8235(7) nm 3, Z =4, R =0 0751. The basic building blocks of the crystal structure included one MoO 5 hexahedron and twelve LaO 6 octahedra which shared a common edge to form a [(La 12 (OH) 12 MoO 29 )] 4- unit. These units were held together by the [(CH 3CH 2) 4N] + ions.展开更多
The isomerization of CH3S（OH）CH2 to CH3S（O）CH3 in the absence and presence of water has been investigated at the G3XMP2//B3LYP/6-311 ＋ G（2df, p） level. The naked isomerization, the reaction without water, gives...The isomerization of CH3S（OH）CH2 to CH3S（O）CH3 in the absence and presence of water has been investigated at the G3XMP2//B3LYP/6-311 ＋ G（2df, p） level. The naked isomerization, the reaction without water, gives the high barrier height （21.56 kcal.mol^-1）. Three models are constructed to describe the water influence on the isomerization, that is, water molecules are the catalyst and the microsolvation, and water molecules act as the catalyst and microsolvation simultaneously. Our results show that the isomerization barrier heights of CH3S（OH）CH2 to CH3S（O）CH3 are reduced by 12.32, 11.04, and 7.80 kcal.mol^-1, respectively, when one, two, and three water molecules are performed as catalyst, in contrast to the naked isomerization. Moreover, the rate constants of the isomerization are calculated using the transition state theory with the Wigner tunneling correction over the temperature range of 240-425 K. We find that the rate constant of a single water molecule as the catalyst is 1.58 times larger than the naked isomerization at 325 K, whereas it is slower by 6 orders of magnitude when water molecule serves as the microsolvation at 325 K, compared to naked reaction. So the water-catalyzed isomerization of CH3S（OH）CH2 to CH3S（O）CH3 is predicted to be the key role in lowering the activation energy. The isomerization involving water molecules acting as mierosolvation is unfavorable under atmospheric conditions.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
基金Supported by the National Natural Science Foundation of China(No.2 0 1710 10 )
文摘A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2 5729(4) nm, b =1 4318(1) nm, c =2 1217(4) nm, β =111 56(1)°, V =6 8235(7) nm 3, Z =4, R =0 0751. The basic building blocks of the crystal structure included one MoO 5 hexahedron and twelve LaO 6 octahedra which shared a common edge to form a [(La 12 (OH) 12 MoO 29 )] 4- unit. These units were held together by the [(CH 3CH 2) 4N] + ions.
基金Acknowledgement This work is supported by the National Natural Science Foundation of China （No. 21173139）, the foundation of Shannxi Education Department （No. 2013JK0667）, and the foundation of Yanan University （No. YDQ2013-16）.
文摘The isomerization of CH3S（OH）CH2 to CH3S（O）CH3 in the absence and presence of water has been investigated at the G3XMP2//B3LYP/6-311 ＋ G（2df, p） level. The naked isomerization, the reaction without water, gives the high barrier height （21.56 kcal.mol^-1）. Three models are constructed to describe the water influence on the isomerization, that is, water molecules are the catalyst and the microsolvation, and water molecules act as the catalyst and microsolvation simultaneously. Our results show that the isomerization barrier heights of CH3S（OH）CH2 to CH3S（O）CH3 are reduced by 12.32, 11.04, and 7.80 kcal.mol^-1, respectively, when one, two, and three water molecules are performed as catalyst, in contrast to the naked isomerization. Moreover, the rate constants of the isomerization are calculated using the transition state theory with the Wigner tunneling correction over the temperature range of 240-425 K. We find that the rate constant of a single water molecule as the catalyst is 1.58 times larger than the naked isomerization at 325 K, whereas it is slower by 6 orders of magnitude when water molecule serves as the microsolvation at 325 K, compared to naked reaction. So the water-catalyzed isomerization of CH3S（OH）CH2 to CH3S（O）CH3 is predicted to be the key role in lowering the activation energy. The isomerization involving water molecules acting as mierosolvation is unfavorable under atmospheric conditions.
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).
