mechanism for the trans to cis isomerization. Evidence to support the mechanism has been obtained by experiments using LiCD3. Thermolysis of cis-PdR2L2 has been demonstrated to proceed through a unimolecular process initiated by a rate-determining dissociation of L to produce a three-coordinate “cis-PdR2L” which reductively eliminates the R groups. Addition of free ligand to the system containing cis-PdMe2L2
制备了一系列具有不同碱度和体积的叔膦配体(L)的反式和顺式二烷基钯(II)配合物,并研究了它们在溶液中的热解和异构化机理。通过使用烷基锂对顺式二烷基异构体选择性形成的原因的检查揭示了一种新型的由烷基锂促进的反式到顺式异构化。提出了涉及形成钯酸三烷基酯中间体的过程作为反式异构化为顺式异构化的机制。已经通过使用 LiCD3 的实验获得了支持该机制的证据。已证明顺式 PdR2L2 的热解是通过单分子过程进行的,该过程由 L 的决定速率解离引发,以产生三配位的“顺式 PdR2L”,该过程还原性地消除了 R 基团。
Fluorophosphonate and alkoxy- and aroxy-fluorophosphine complexes of platinum(II) and palladium(II). Part I. Reactions of complexes of tertiary phosphines with alkoxy- and aroxy-difluorophosphines
作者:J�rgen Grosse、Reinhard Schmutzler
DOI:10.1039/dt9760000405
日期:——
Michaelis–Arbuzov type reaction from [MCl2L2] and PF2(OR)(R = allyl, Prn, or Bun). Preparation of complexes cis-[MCl2(PEt3)PF2(OR)}](M = Pt or Pd; R = Bun or Ph) and chloro-bridged binuclear complexes [MCl(PEt3)(PF2O)}2] is also reported. Substituent redistribution reactions of PF2(OR) have been observed under the influence of the transition metal, M. Fluorine-19 and 31P n.m.r., i.r., and, in part, mass-spectroscopic
通过Michaelis-Arbuzov型反应制备了一系列反式-[MClL 2(PF 2 O)](M = Pt或Pd; L = PEt 3 – n Ph n;n = 0-3)的二氟膦酸酯络合物。 [MCl 2 L 2 ]和PF 2(OR)(R =烯丙基,Pr n或Bu n)。制备顺式-[MCl 2(PEt 3)PF 2(OR)}](M = Pt或Pd; R = Bu n或Ph)和氯桥联双核络合物[MCl(PEt 3)(PF 2O)} 2 ]也被报告。在过渡金属M的影响下,观察到了PF 2(OR)的取代基再分布反应。氟19和31 P nmr,ir,部分报道了新配合物的质谱数据,并在中讨论了。所获得产品结构的术语。
Reactivity of BH3 and 9-BBN towards palladium(II) complexes of diphenylvinyl- and diphenylallyl-phosphine; X-ray structures of [PdCl2(PPh2CH2CH2CH3)]2 and [PdCl2(PPh2CH2CHCH2)]2
作者:Simon J. Coles、Paul Faulds、Michael B. Hursthouse、David G. Kelly、Georgia C. Ranger、Andrew J. Toner、Neil M. Walker
DOI:10.1016/s0022-328x(99)00283-1
日期:1999.9
Palladium(II) chloride complexes PdCl2L2 and [PdCl2L]2 have been prepared with the phosphine ligands PPh2CHCH2 and PPh2CH2CHCH2. The reactions of PdCl2L2 complexes with thf·BH3 afford equilibria in which the components may be identified by 31P1H}-NMR spectroscopy. PdCl2L2 and [PdCl2L]2 complexes and phosphine–borane adducts are observed. In addition, analogues of the PdCl2L2 and [PdCl2L]2 complexes