Stabilization of an Electron-Unsaturated Pd(I)–Pd(I) Unit by Double Hemichelation
Stabilization of an Electron-Unsaturated Pd(I)–Pd(I) Unit by Double Hemichelation
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双半螯合作用稳定电子不饱和 Pd(I)–Pd(I) 单元
DOI：
10.1021/acs.organomet.5b00349
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发表时间：
2015
期刊：
影响因子：
2.8
通讯作者：
J. Djukic
中科院分区：
文献类型：
--
作者：
C. Werlé;L. Karmazin;C. Bailly;L. Ricard;J. Djukic
通过三羰基（η6-3-苯基丙-1-烯基）铬阴离子与μ-氯桥钯环的反应，探讨了三种不同钯环的Pd（II）中心的常规配位和半螯合之间的竞争.结构X射线衍射分析表明，反应的主要产物为传统的（η3-烯丙基）Pd（II）配合物。后者显示显着的动态行为，在溶液中，建议由1H NMR光谱。根据DFT计算，这种动态行为可以与构象平衡和可能的化学交换导致Pd（II）hemichelates。（η3-烯丙基）Pd（II）配合物通过还原性缩合反应容易地转化为Pd（II）的均配双螯合物和Pd（I）-Pd（I）单元的双半螯合物。后者具有与文献中的电子饱和双（μ-烯丙基）桥联Pd（I）配合物非常相似的结构特征：Pd-Pd相互作用仅为弱共价作用，且主要是单电子键。
The competition between conventional coordination and hemichelation of a Pd(II) center of three different palladacycles was probed by reacting the tricarbonyl(η6-3-phenylprop-1-enyl)chromium anion with μ-chloro-bridged palladacycles. Structural X-ray diffraction analysis indicates that the main products of the reaction are conventional (η3-allyl)Pd(II) complexes. The latter display significant dynamic behavior in solution, as suggested by 1H NMR spectroscopy. According to DFT calculations this dynamic behavior can be related to conformational equilibria and to possible chemical exchanges leading to Pd(II) hemichelates. The (η3-allyl)Pd(II) complexes convert readily to homoleptic bis-chelates of Pd(II) and to a bis-hemichelate of a Pd(I)–Pd(I) unit via a reductive disproportionation reaction. The latter Pd(I)–Pd(I) complex bears structural features very similar to those of electron-saturated bis(μ-allyl)-bridged Pd(I) complexes in the literature: the Pd–Pd interaction is only weakly covalent and is dominat...
影响因子：
5.5
作者：
Contreras-Garcia, Julia;Johnson, Erin R.;Keinan, Shahar;Chaudret, Robin;Piquemal, Jean-Philip;Beratan, David N.;Yang, Weitao
通讯作者：
Yang, Weitao
影响因子：
15
作者：
Johnson ER;Keinan S;Mori-Sánchez P;Contreras-García J;Cohen AJ;Yang W
通讯作者：
Yang W