A single-crystal ESR and quantum chemical study of electron-capture trialkylphosphine sulfide and selenide radical anions with a three-electron bond
作者:Rene A. J. Janssen、Joost A. J. M. Kingma、Henk M. Buck
DOI:10.1021/ja00218a004
日期:1988.5
A low-temperature ESRstudy of electron-capture phosphoranyl radicals in X-irradiated single crystals of tri- alkylphosphine sulfides and selenides (R3PX: X = S, Se; R = CH3, C2HS, C&l,) is presented. The principal values and direction cosines of the g tensors and ,'P and "Se hyperfine coupling tensors are determined and correlated with the X-ray structure analysis of the parent compounds. All studied
介绍了对三烷基膦硫化物和硒化物(R3PX:X = S、Se;R = CH3、C2HS、C&1)的 X 辐照单晶中电子捕获磷酰基自由基的低温 ESR 研究。g 张量和 ,'P 和 "Se 超精细耦合张量的主值和方向余弦被确定并与母体化合物的 X 射线结构分析相关。所有研究的化合物都揭示了 R3PX-自由基阴离子的形成,与三电子 PLX 键,其中未配对电子几乎均匀分布在磷和取代基 X 上。 结果表明,自由基的位点对称性对应于前体分子的结晶点对称性,从而产生纯三角 (C3) (C2HS)、PX- 和 C 的自由基,(CH,)、PX- 和 (C6H11)3PX- 的对称性。模型 H$S- 上的 Ab initio 量子化学计算(4-31G* SCF 和 CASSCF)预测三电子键不稳定并解离为 PH 和 SO-。计算并未重现实验耦合和观察到的自旋密度分布,但倾向于将未配对电子完全定位在硫上。这种缺
Reactions of Group V Metal Compounds with Sulfur Trioxide
作者:Fumio Ando、Jugo Koketsu、Yoshio Ishii
DOI:10.1246/bcsj.54.3495
日期:1981.11
Trialkylphosphines react with equimolar amounts of sulfurtrioxide to form the 1:1 adducts R3P⊕–SO3\ominus. Trialkylarsines and -stibines undergo sulfurtrioxide insertion reactions across the metal-carbon bond to give the trisulfonates of the metal M(OSO2R)3 (M=As, Sb). The reactions of trialkyl phosphites, with sulfurtrioxide yield trialkyl phosphates, trialkyl thiophosphates, dialkyl alkylphosphonates
Preparation and catalytic activity of cationic rhodium(I) and iridium(I) complexes with phosphine sulphide ligands
作者:C. Claver、F. Gili、J. Viñas、A. Ruiz
DOI:10.1016/s0277-5387(00)80891-8
日期:1987.1
The preparation and properties of cationicrhodium and iridiumcomplexes of types [M(diolefin)L2](ClO4) and [M(diolefin)L(PPh3)](ClO4) [M = Rh, diolefin = 1,5-cyclooctadiene (COD) or 2,5-norbornadiene; M = Ir, diolefin = COD; L = phosphine sulphide] are described. The complexes have been characterized by IR, 1H NMR and 31P NMR spectroscopy. The use of [M(diolefin)L2](ClO4) as catalyst precursors in
[M(二烯烃)L 2 ](ClO 4)和[M(二烯烃)L(PPh 3)](ClO 4)型阳离子铑和铱配合物的制备和性质[M = Rh,二烯烃= 1,5 -环辛二烯(COD)或2,5-降冰片二烯; M = Ir,二烯烃= COD;描述了L =硫化膦。该复合物已通过IR,1 H NMR和31 P NMR光谱表征。研究了[M(二烯烃)L 2 ](ClO 4)在烯烃均相加氢中作为催化剂前体的应用。
Structure and equilibria in triorganolead halide adduct formation
作者:Hilary J. Eppley、James L. Ealy、Claude H. Yoder、J.N. Spencer、Arnold L. Rheingold
DOI:10.1016/0022-328x(92)80112-b
日期:1992.6
paralleled the trend reported previously for organotin halides. The equilibrium constant for adduct formation with triphenylphosphine oxide (TPPO) is slightly larger for triphenyllead chloride relative to triphenyltin chloride, confirming the expected increase in acidities down Group 14. X-Ray diffraction studies of triphenylphosphine oxide adducts of triphenyllead bromide and triphenyltin chloride showed
Catalytic Degradation of Sulfur Hexafluoride by Rhodium Complexes
作者:Lada Zámostná、Thomas Braun
DOI:10.1002/anie.201505462
日期:2015.9.1
potent greenhouse gases. SF6 is thermally and chemically extremely inert, and therefore, it has been used in various industrial applications. However, this inertness results in a major challenge for its depletion. We report on a process for a catalytic degradation of SF6 in the homogeneous phase by using rhodium complexes as precatalysts. The SF6 activation reactions feature mild reaction conditions, low