超快泵浦-探针光谱法(λ泵 = 420 nm)用于研究PtBr62-络合物的光化。激发至d–d激发的1 T 1g态,随后形成中间吸收衰减,其特征时间分别为370 fs,2.2和15.2 ps。两次较短的时间归因于低激发态的形成(3 T 1g)以及其振动冷却伴随溶剂松弛。最长的时间被解释为3 T 1g转变为热基态(1 A 1g)和离解产物(PtBr 5(H 2O)-复数)。该方案与光化量子产率在激发波长上的独立性相一致。
作者:E. M. Glebov、V. F. Plyusnin、V. P. Grivin、A. B. Venediktov、S. V. Korenev
DOI:10.1007/s11172-007-0375-7
日期:2007.12
Photochemistry of the PtBr62− complex in aqueous solution was studied by steady-state and laser flashphotolysis (308 nm). The multistep photoaquation of the complex occurs in the nano-and microsecond time intervals without the formation of intermediate platinum(III) complexes.
Kinetics and mechanism for reduction of halo- and haloam(m)ine platinum(IV) complexes by l-ascorbate
作者:Kelemu Lemma、Donald A. House、Negussie Retta、Lars I. Elding
DOI:10.1016/s0020-1693(01)00762-9
日期:2002.3
The redox reactions follow the rate law: -d[Pt(IV]/dt = k[H(2)Asc](tot)[Pt(IV)] where k is a pH-dependent second-order rate constant and [H(2)Asc](tot), the total concentration of ascorbicacid. The pH-dependence of k is attributed to parallel reduction of Pt(IV) by the protolytic species HAsc(-) and Asc(2-). Analysis of the kinetics data reveals that the ascorbate anion Asc(2-) is up to seven orders
还原模型铂(IV)配合物顺-[PtCl4(NH3)(2)](1),反式-[PtCl4(NH3)(2)](2)。反式-[PtCl2(en)(2)](2+)(3),反式[[PtBr2(NH3)(4)](2+)(4),[PtCl6](2-)(5)和研究了使用L-抗坏血酸(H(2)Asc)在25°C下1.0 M水性介质中于1.75小于或等于pH小于或等于7.20的区域中的[PtBr6](2-)(6)。停止流式分光光度法。氧化还原反应遵循速率定律:-d [Pt(IV)/ dt = k [H(2)Asc](tot)[Pt(IV)],其中k是pH依赖的二级速率常数,[H] (2)Asc](tot),抗坏血酸的总浓度,k的pH依赖性归因于蛋白水解物质HAsc(-)和Asc(2-)平行还原Pt(IV)。动力学数据分析表明,抗坏血酸阴离子Asc(2-)的反应性比HAsc(-)高7个数量级,而H(2)Asc无反应性。从HAsc(-)/
Bromide anation kinetics for some platinum(IV) bromo aqua complexes
作者:L.I. Elding、L. Gustafson
DOI:10.1016/s0020-1693(00)90919-8
日期:1977.1
Abstract Bromide anations of PtBr 5 H 2 O − in the presence of PtBr 2− 4 or bromine, of trans -PtBr 4 (H 2 O) 2 in the presence of PtBr 2− 4 and of cis -PtBr 4 (H 2 O) 2 in the presence of bromine have been studied in 0.50 M perchloric acid medium at 25 °C. The rate law for the bromide anation of PtBr 5 H 2 O − indicates two parallel reaction paths. The term k′Br − ] 2 corresponds to a bromide assisted
Precipitation and liquidâliquid extraction of PtX62â (X = Clâ, Brâ, SCNâ) in acidified aqueous solutions ranging from 0.1 M to 9 M HBr or 11 M of HCl have been studied using water-soluble or hydrophobic ionic liquids. Divalent hexachloroplatinate(IV) anions appear to be extracted much less efficiently than tetrachloroaurate(III) complexes. At a concentration of 11 M HCl, values of 15 and 800 for the distribution coefficients of PtCl62â and PtBr62â in [OMIM][NTf2] have been obtained accordingly. The presence of a labile hydrogen on the imidazolium ring has been found to play a specific role in the extraction of platinum(IV) complexes in concentrated HCl or HBr. Pt(SCN)62â appears to be very efficiently extracted at pH 1 using [OMIM][NTf2], exhibiting a distribution coefficient of 6150. Finally, two methods for quantitative separation of gold and platinum in water using in each method two extraction steps have been proposed. The back extraction of platinum(IV) during the second separation process was also discussed.
使用水溶性或疏水性离子液体研究了在0.1 M至9 M HBr或11 M HCl的酸化水溶液中PtX62∘(X = Cl∘、Br∘、SCN∘)的沉淀和液-液萃取。二价六氯铂酸根阴离子的萃取效率似乎远低于四氯金酸根(III)络合物。在11 M HCl的浓度下,PtCl62∘和PtBr62∘在[OMIM][NTf2]中的分配系数分别为15和800。研究发现,在浓HCl或HBr中,咪唑环上不稳定的氢在铂(IV)络合物的萃取中起着特殊的作用。在pH 1下,Pt(SCN)62∘似乎非常有效地被[OMIM][NTf2]萃取,分配系数为6150。最后,提出了两种定量分离水中金和铂的方法,每种方法都包含两个萃取步骤。还讨论了在第二次分离过程中铂(IV)的逆向萃取。