The addition of halogens and interhalogens on palladacyclopentadienyl complexes bearing quinolyl-thioether as spectator ligands. A kinetic and computational study
in excess induces the extrusion of the di-bromo-(E, E)-σ-butadiene and the formation of the thioquinoline palladium(II) di-bromide species. The kinetics and mechanism of these reactions have been determined. Except for one case which was analyzed in detail by a computational study, the oxidative addition of the interhalogens ICl and IBr yields the species that is less predictable from the thermodynamic
The addition of bromine and iodine to palladacyclopentadienyl complexes bearing bidentate heteroditopic P−N spectator ligands derived from differently substituted quinolinic frames. The unexpected evolution of the reaction
complex reacts with I2. Furthermore, we have obtained exclusively an unprecedented zwitterionic complex when I2 reacts with the palladacyclopentadienyl complex bearing the substituted quinoline and a different ratio of an equilibrium mixture of σ-butadienyl and the zwitterionic species when the latter derivative reacts with Br2. The solid state structures of one σ-butadienyl complex and of the two novel
Role of the Ligand and of the Size and Flexibility of the Palladium−Ancillary Ligand Cycle on the Reactivity of Substituted Alkynes toward Palladium(0) Complexes Bearing Potentially Terdentate Nitrogen−Sulfur−Nitrogen or Nitrogen−Nitrogen−Nitrogen Ligands: Kinetic and Structural Study
palladium(0) complexes bearing potentiallyterdentateligands and dimethyl acetylenedicarboxylate (DMA) to give the corresponding palladacyclopentadiene complexes was studied under kinetic conditions. The reactivity of the complexes was markedly influenced by the nature of the ancillary ligand. Thus, when pyridyldithioether (SNS) and dipyridylthioether (NSN) ligands are used, the reactivity and the
Palladacyclopentadienyl complexes bearing purine‐based N‐heterocyclic carbenes: A new class of promising antiproliferative agents against human ovarian cancer
A complete protocol for the synthesis of new palladacyclopentadienyl complexes with purine‐based carbenes as supporting ligands is described. The new organometallic compounds were exhaustively characterized using NMR and infrared spectroscopies and elemental analysis. The single‐crystal X‐ray structure of complex 2b coordinating also a triphenylphosphine was resolved. Some of these complexes showed
Attack of molecular iodine to novel palladacyclopentadienyl complexes bearing isocyanides as spectator ligands. A computational and mechanistic study
作者:Luciano Canovese、Fabiano Visentin、Cladio Santo
DOI:10.1016/j.jorganchem.2014.07.012
日期:2014.11
butadienyl fragment σ-coordinated, and the isocyanides cis to each other which eventually isomerizes to the final trans product. The reaction rates related to the formation of the cis derivatives (k1) and to the isomerization process (k1′) were determined as refined parameters of the non linear regression analysis of the monoexponential relationship which is a function of the UV–vis spectral changes
我们已经合成了一些带有2,6-二甲基苯并,2-甲苯基和叔丁基异氰酸酯(分别为DIC,TOSMIC和TIC)作为配体的palladacyclopentadienyl配合物。将I 2氧化加到DIC衍生物中,生成的复合物带有碘,σ-配位的丁二烯片段和互反位的异氰酸酯作为最终物质。在通过UV-vis和1进行的动力学研究的基础上1 H NMR技术我们提出了一个合理的机制,该机制与其他作者对相似化合物进行的计算研究相符,并通过我们执行的计算方法得到了证实。所提出的机制表明形成了在子午位置带有两个碘的Pd(IV)八面体中间络合物。后者产生另一种带有碘的中间体配合物,其碘配位的开放式丁二烯片段和异氰酸酯彼此顺式,最终异构化为最终的反式产物。反应速率与顺式衍生物(k 1)的形成和异构化过程有关(ķ1个′) 确定作为单指数关系的非线性回归分析的精确参数,该参数是UV-vis光谱变化和时间的函数。