Studies of lambert's reaction: The formation of [Mn2(CO)8(μ-AsR2)2] complexes from tertiary arsines and [Mn2(CO)10] at high temperatures
作者:Henry Ashton、Brídín Brady、A.R. Manning
DOI:10.1016/s0022-328x(00)81030-x
日期:1981.11
or As) are inert, the normal photochemical or thermal reaction of tertiaryphosphines or arsines, L, with [Mn2(CO)10] is CO substitution with the formation of [Mn2(CO)8(L)2] derivatives (I). At elevated temperatures some triarylarsines, R3As, undergo Lambert's reaction with ligand fragmentation to give [Mn2(CO)8(μ-AsR2)2] complexes (II) (R = Ph, p-MeOC6H4, p-FC6H4, or p-CIC6H4) even though, in the absence
虽然非常大体积配体例如(ø -MeC 6 ħ 4)3 E或(μ-C 10 H ^ 7)3 E(E = P或As)是惰性的,正常的光化学或叔膦或胂,L的热反应, [Mn 2(CO)10 ]与[Mn 2(CO)8(L)2 ]衍生物(I)的形成中的CO被取代。在升高的温度下的一些triarylarsines,R 3如,经历Lambert的反应与配体碎片,得到[锰2(CO)8(μ-ASR 2)2即使没有[Mn 2(CO)10 ] R 3 As的情况,也可以使用]配合物(II)(R = Ph,p -MeOC 6 H 4,p -FC 6 H 4或p- CIC 6 H 4)。在相同条件下稳定。(p -Me 2 NC 6 H 4)3- As表现出优异的行为,形成I型产物;通过一些HN(C 6 H 4)2由于失去了非芳基R = PhCH 2,环-C 6 H 11或MeO而得到II型产物的AsR ;和通过pH(α-C
Synthesis and characterisation of new triple halide-bridged mixed valence binuclear complexes of ruthenium and osmium
Several isomers of the type [M2Cl5L4] (M = Ru, L = AsPh3, As(p-tol)3, As(p-PhCl)3, PEt2Ph, PMe2Ph; L2 = Ph2As(CH2)2AsPh2; M = Os, L = PPh3, AsPh3) have been synthesised by various routes and characterised by magnetic, ESR and electrochemical measurements, and for [(PEt2Ph)Cl2RuCl3Ru(PEt2Ph)3] by X-ray structural analysis.
An improved bidentate complex of iridium as a catalyst for hydrogen isotope exchange
作者:John M. Herbert、Andrew D. Kohler、Alan H. McNeill
DOI:10.1002/jlcr.921
日期:2005.3.30
Iridium(I) complexes 1, containing bidentate phosphines, and 3, with arsine ligands, are generated in situ. These species mediate hydrogenisotopeexchange in a variety of aromatic substrates including benzyl ketones. Although the catalytic activities of complexes 1 and 3 are generally unexceptional, a logical step leads to the use of [ethylene-1,2-bis(diphenylarsine)](cyclooctadiene)iridium(I) tetrafluoroborate
Synthesis, properties and application of electronically-tuned tetraarylarsonium salts as phase transfer catalysts (PTC) for the synthesis of gem -difluorocyclopropanes
作者:Krzysztof Grudzień、Tymoteusz Basak、Michał Barbasiewicz、Tomasz M. Wojciechowski、Michał Fedoryński
DOI:10.1016/j.jfluchem.2017.03.014
日期:2017.5
Preparation of gem-difluorocyclopropane from α-methylstyrene and chlorodifluoromethane was investigated under basic two-phase conditions. Although simple tetraalkylammonium salts appeared uneffective as phase-transfer catalysts (PTC) for this purpose, tetraphenylarsonium chloride displayed moderate activity, and inspired studies of the phenomena. To improve its efficiency we synthesized set of electronically-tuned
Kinetics, Mechanism, and Computational Studies of Rhenium-Catalyzed Desulfurization Reactions of Thiiranes (Thioepoxides)
作者:Abdellatif Ibdah、William S. Jenks、James H. Espenson
DOI:10.1021/ic0521426
日期:2006.7.1
catalyzes S atom transfer from thiiranes to triarylphosphines and triarylarsines. Despite the fact that phosphines are more nucleophilic than arsines, phosphines are less effective because they rapidly convert the dimer catalyst to the much less reactive catalyst [MeReO(edt)(PAr3)] (2). With AsAr3, which does not yield the monomer, the rate law is given by v = k[thiirane][1], independent of the arsine
氧化or(V)二聚体MeReO(edt)} 2(1;其中edt = 1,2-乙二硫代硫酸盐)催化S原子从硫烷转移至三芳基膦和三芳基赖氨酸。尽管磷化氢比砷化氢更具亲核性,但磷化氢却效率较低,因为它们会迅速将二聚体催化剂转化为反应性低得多的催化剂[MeReO(edt)(PAr3)](2)。对于不产生单体的AsAr3,速率法则由v = k [thirirane] [1]给出,而与the浓度无关。CDCl3中25.0摄氏度下k的值为环己烯硫醚的5.58 +/- 0.08 L mol(-1)s(-1)和ca. 硫化丙烯为2 L mol(-1)s(-1)。环己烯硫醚的活化参数为deltaH(双匕首)= 10.0 +/- 0.9 kcal mol(-1)和deltaS(double dagger)= -21 +/- 3 cal K(-1)mol(-1)。s氨酸在控制速率释放烯烃后进入催化循环,它与Re