The synthesis of a triphosphenium bromide salt is described and its use as a P+ transfer agent is outlined by reactions with an N-heterocyclic carbene and an anionic bisphosphine, yielding an NHC-stabilized P(I) cation and a P(I) containing zwitterion, respectively.
Abstract
我们在此提出一个triphosphenium溴化物盐的优化合成。除了是一种多功能复分解试剂,这种异常稳定含有低原子价磷化合物作为一种有用的 P +转移剂。不同于传统的方法中使用以访问低坐标磷物种通常需要自燃含磷前体(白磷,三(三甲基甲硅烷)膦等 ),或苛刻还原剂(碱金属,钾石墨等 ),目前方法不涉及引火或爆炸性的试剂,并可以在良好的收益大尺度(> 20克)通过大学生基本无空气的合成训练来完成。溴化物抗衡离子可容易地使用典型的盐复分解试剂以获得具有所需性质和反应性材料以外的阴离子,例如四苯基硼酸盐(本文中所描述)交换。这种P +转让的多功能性接近角通过用N-杂环卡宾和阴离子双膦,其中每一个容易置换中性二膦,得到NHC稳定磷(I)的含有两性离子的阳离子和磷(I)中,分别这些triphosphenium前体的反应例举。
注:氘代溶剂根据文献程序在必要时,所有其它溶剂干燥的一系列Grubbs'型柱12和在使用之前脱气干燥。钾1,2,4-三(二苯基膦基)环戊二烯[K] [(PH 2×P)3 C 5 H 2]和N-杂环卡宾-1,3,4,5- tetramethylimidazole -2-亚基( 我 NHC 我 )根据文献方法合成的,后者在使用前升华。9,13环己烯经氢化钙2上干燥,蒸馏,使用前脱气。乙腈- d 3<…
The authors thank the Natural Sciences and Engineering Research Council (NSERC) of Canada and the Canada Foundation for Innovation (CFI) for funding and scholarship support.
Materials
bis(diphenyl)phosphino ethane (dppe)
Strem
1663-45-2
98% Stored in gloved box, used as is.
Anhydrous Dichloromethane (DCM)
Sigma Aldrich
270997
Purified through solvent purification system, or standard methods
Anhydrous Cyclohexene
Sigma Aldrich
29240
Dried over calcium hydride and distilled.
Phosphorus Tribromide (PBr3)
Sigma Aldrich
157783
99% Stored in glove box, used as is. Air sensitive
Anyhydrous Tetrahydrofuran (THF)
Sigma Aldrich
401757
Purified through solvent purification system, or standard methods
Methylene Chloride-D2 (CD2Cl2)
Sigma Aldrich
DLM-23-25
Dried over phosphorus pentoxide, vacuum transferred or distilled
Acetonitrile
Alfa Aesar
5/8/1975
Stored in glove box, used as is
Sodium Tetraphenylborate
Sigma Aldrich
T25402
Stored in glove box, used as is
Anyhydrous Diethyl Ether
Sigma Aldrich
673811
Purified through solvent purification system, or standard methods
Anhydrous Pentane
Sigma Aldrich
236705
Purified through solvent purification system, or standard methods
Kosnik, S. C., Binder, J. F., Nascimento, M. C., Macdonald, C. L. B. Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I). J. Vis. Exp. (117), e55021, doi:10.3791/55021 (2016).