Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications
Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications
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锍双阳离子的制备、结构分析和反应性研究
DOI：
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
D. Vidović
中科院分区：
文献类型：
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作者：
Madelyn Qin Yi Tay;G. Ilić;U. Werner‐Zwanziger;Yunpeng Lu;Rakesh Ganguly;L. Ricard;G. Frison;D. Carmichael;D. Vidović
这项工作扩展了最近合成的两坐标含P（III）的反应性[((Ph3P)2C)P(NiPr2)]2+ (3a2+)。通式[((RPh2P)2C)P(NR ' 2)]2+ (3b2+, R = 1/2 (CH2)3, R ' = iPr]的两个附加指示；制备了3c2+， R = Ph, R ' = Cy)。溶液和固态31P核磁共振各向同性位移在360 ppm左右被观察到。除[3a][SbF6]2外，31P CP/MAS NMR谱显示固态中指示位点周围存在高度的结构无序。令人惊讶的是，只有在AlCl4 -、SbF6 -和取代的四芳基硼酸盐存在的情况下，才有可能合成3a2+，而使用ClO4 -、OTf -、BF4 -、PF6 -和BPh4 -则会产生复杂的产物混合物。单晶x射线分析表明，3a2+和3c2+为中心CPN片段的4π类烯丙基结构，这已通过详细的理论研究得到支持。适应症3a2+/3c2+和PMe3之间的初步反应性研究表明：
This work expands on the recent synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)2C)P(NiPr2)]2+ (3a2+). Two additional dications of general formula [((RPh2P)2C)P(NR′2)]2+ (3b2+, R = 1/2 (CH2)3, R′ = iPr; 3c2+, R = Ph, R′ = Cy) have been prepared. Solution and solid-state 31P NMR isotropic shifts for this dication class were observed around 360 ppm. Except for [3a][SbF6]2, the 31P CP/MAS NMR spectra reveal a high degree of structural disorder around the dicationic site in the solid state. Surprisingly, the synthesis of dication 3a2+ was only possible in the presence of AlCl4–, SbF6–, and substituted tetraarylborates, while the use of ClO4–, OTf–, BF4–, PF6–, and BPh4– resulted in complex product mixtures. Single-crystal X-ray analysis of dications 3a2+ and 3c2+ suggested a 4π allyl-like structure for the central CPN fragment, and this has been supported through detailed theoretical investigations. Initial reactivity studies between dications 3a2+/3c2+ and PMe3 show an equil...
卡宾稳定的磷 (III) 中心阳离子 [LPX(2)]( ) 和 [L(2)PX](2 )（L = NHC；X = Cl、CN、N(3)）
影响因子：
15
作者：
J. J. Weigand;K.-O. Feldmann;F. D. Henne
通讯作者：
F. D. Henne
影响因子：
15
作者：
Li, Yan;Mondal, Kartik Chandra;Andrada, Diego M.
通讯作者：
Andrada, Diego M.