Darstellung und reaktionen von diphosphen-komplexen RPPR[M(CO)5]3 (M = Cr, Mo, W)
作者:Gottfried Huttner、Jutta Borm、Laszlo Zsolnai
DOI:10.1016/0022-328x(86)80149-8
日期:1986.5
Decacarbonyldimetallates Na2M2(CO)10 (M = Cr, Mo, W) react with dihalophosphanes, (R)P(Cl)2, to yield trinuclear diphosphene complexes of the form RPPR[M(CO)5]3. The by-products of these reactions are diphosphane- and phosphido-bridged complexes.
十羰基二金属盐Na 2 M 2(CO)10(M = Cr,Mo,W)与二卤代膦烷(R)P(Cl)2反应,生成RPPR[M(CO)5 ] 3形式的三核二膦配合物。这些反应的副产物是二膦-和磷-桥联的配合物。
Sequential electrophilic P–C bond formation in metal-coordinated chlorophosphines
作者:Arumugam Jayaraman、Tyler V. Jacob、Jeff Bisskey、Brian T. Sterenberg
DOI:10.1039/c5dt01281c
日期:——
Metal-coordinated chlorophosphines undergo facile sequential electrophilic substitution reactions, stepwise or in one-pot reactions, to form phosphines with three different substituents.
Alkyne Insertion into P–C(sp<sup>2</sup>) Bonds as a Route to Fused Phospholes: Transition-Metal-Like Reactivity at Phosphorus
作者:Shrikant Nilewar、Arumugam Jayaraman、Brian T. Sterenberg
DOI:10.1021/acs.organomet.8b00718
日期:2018.12.24
While alkyne insertion into metal–carbon(sp2) bonds is common in transition metal chemistry, direct alkyne insertions into E–C(sp2) bonds are very rare in main group chemistry. Herein, we report a direct alkyne insertionreaction into the P–C(aryl) bonds of tungsten-coordinated phenyl-aryl phosphenium ions, which lead to phenyl-vinyl phosphenium ions. The insertionreaction is followed by electrophilic
虽然在过渡金属化学中,炔烃通常会插入到金属-碳(sp 2)键中,但直接在炔烃化学中直接将炔烃插入到E-C(sp 2)键中是非常罕见的。在本文中,我们报道了炔烃直接插入钨配位的苯基-芳基离子的P–C(芳基)键中,从而导致苯基-乙烯基离子。插入反应后,将ion离子亲电取代到芳基上,从而导致净环化反应并形成芳烃和杂芳烃稠合的磷脂。产品的区域选择性和计算化学已用于阐明插入亲电取代机理。该方法已用于合成已知的苯并磷脂和磷[3,2-b ]噻吩和新的磷[3,2- b ]吡咯,磷[2,3- b ]吡咯和磷[2,3- b ]吲哚环系统。
Synthesis of 1,1′‐bisphosphinoferrocenes using electrophilic addition reactions of tungsten coordinated phosphenium ions and phosphine triflates
作者:Hamdi F.K. Bumraiwha、Brian T. Sterenberg
DOI:10.1016/j.jorganchem.2022.122511
日期:2022.12
[W(CO)5]-coordinated phosphine triflates undergo electrophilic substitution reactions with ferrocene. We have used this methodology to add PPh2 and PPhCl units to the 1 and 1′ positions of ferrocene to form tungsten pentacarbonyl complexes of 1,1′-bisdiphenylphosphinoferrocene, 1,1′-bischlorophenylphosphinoferrocene, and 1-diphenylphosphino-1′-chlorophenylphosphinoferrocene. The chlorophenylphosphinoferrocenes
[W(CO) 5 ]-配位膦三氟甲磺酸酯与二茂铁发生亲电取代反应。我们使用这种方法将 PPh 2和 PPhCl 单元添加到二茂铁的 1 和 1' 位置以形成 1,1'-双二苯基膦基二茂铁、1,1'-双氯苯基膦基二茂铁和 1-二苯基膦基-1'-氯苯基膦基二茂铁的五羰基钨配合物. 氯苯基膦基二茂铁可以转化为膦三氟甲磺酸酯,并进行进一步的亲电取代,使我们能够引入额外的二茂铁基、烯丙基和炔基,形成 C 10 H 8 Fe(PPh 2 )(PPhR) 和 C 10 H 8的五羰基钨配合物铁(PPhR)2 ( R = 烯丙基、苯炔基、二茂铁基)。
Versatile behavior of hydrido monometallic or heterobimetallic carbonyl anions toward dichlorophosphines and 1,1-dichlorodiphosphines
作者:Hermann Westermann、Martin Nieger、Edgar Niecke、Jean Pierre Majoral、Anne Marie Caminade、Rene Mathieu、Erhard Irmer