制备及反应性的Triphosphenium溴化物盐：磷方便稳定来源（I）
Summary
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。
Introduction
在非常低的氧化或价态主族元素的化学已从其独特的粘合和结构引起的根本利益，在过去的二十年一直显著兴趣的领域。1除了，这些化合物常常显示从非常不同的反应性他们那些较为典型的氧化态同行。在这个意义上说，他们提供显著潜力试剂建造更复杂的主基团的元素的材料。
含分子具有里程碑意义的类低价的磷是这是首次由Schmidpeter 20世纪80年代报“triphosphenium”阳离子。2这些离子配有两个phosphonio取代连接一个dicoordinate磷（I）离子，具有更稳定的变种从建。螯合框架3,4我们集团优化triphosphenium卤盐的合成5 – 7，具有证明，这些稳定化合物是对于磷（I）的受控合成有用多功能P +转移剂的含低聚物，8两性离子，9和phosphamethine花青染料。-10,11-虽然这类化合物的原始合成通常涉及危险磷含的试剂和/或高度减小条件下，我们目前的控制路线是安全的，P-原子高效，方便。在高纯度材料的方法，结果可使用的染料，配体对过渡金属配合物和用于更复杂的含磷物质的前体。
Protocol
Representative Results
Discussion
为报告，以确认连接的所有产品，得到的晶体结构和多核NMR（31 P，1 H和13 C）。电电离质谱分析法被用来确认阳离子的存在和用元素分析来确认样品的分析纯度。
至关重要的是，所有的反应是在干燥的无空气的环境中进行，以确保没有意外的副产物或分解产物形成的。使用DPPE略有过剩，以及环己烯的过量（10当量）是必要的，以确保[dppeP] [BR]良好收益…
Divulgations
The authors have nothing to disclose.
Acknowledgements
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 |
References
- Macdonald, C. L. B., Ellis, B. D., Swidan, A. Low-Oxidation-State Main Group Compounds. Encyclopedia of Inorganic and Bioinorganic Chemistry. , (2011).
- Coffer (née Monks), P. K., Dillon, K. B. Cyclic triphosphenium ions and related species. Coord. Chem. Rev. 257 (5-6), 910-923 (2013).
- Schmidpeter, A., Lochschmidt, S. New Products from PCl3, P(NMe2)3, and AlCl3. Angew. Chem. Internat. Ed. in Engl. 25 (3), 253-254 (1986).
- Schmidpeter, A., Lochschmidt, S., Karaghiosoff, K., Sheldrickb, W. S. Triphosphane-l,3-di-ium Ions. J. Chem. Soc. Chem. Commun. , 1447-1448 (1985).
- Ellis, B. D., Carlesimo, M., Macdonald, C. L. B. Stabilised phosphorus(I) and arsenic(I) iodide: readily-synthesised reagents for low oxidation state main group chemistry. Chem. Commun. 15 (15), 1946-1947 (2003).
- Norton, E. L., Szekely, K. L. S., Dube, J. W., Bomben, P. G., Macdonald, C. L. B. A convenient preparative method for cyclic triphosphenium bromide and chloride salts. Inorg. Chem. 47 (3), 1196-1203 (2008).
- Ellis, B. D., Macdonald, C. L. B. Phosphorus(I) iodide: a versatile metathesis reagent for the synthesis of low oxidation state phosphorus compounds. Inorg. Chem. 45 (17), 6864-6874 (2006).
- Kosnik, S. C., Farrar, G. J., Norton, E. L., Cooper, B. F. T., Ellis, B. D., Macdonald, C. L. B. Low-Valent Chemistry: An Alternative Approach to Phosphorus- Containing Oligomers. Inorg. Chem. 11 (53), 13061-13069 (2014).
- Kosnik, S. C., Macdonald, C. L. B. A zwitterionic triphosphenium compound as a tunable multifunctional donor. Dalton Trans. 45 (14), 6251-6258 (2016).
- Binder, J. F., Swidan, A., Tang, M., Nguyen, J. H., Macdonald, C. L. B. Remarkably stable chelating bis-N-heterocyclic carbene adducts of phosphorus(I) cations. Chem. Commun. 51 (36), 7741-7744 (2015).
- Binder, J. F., Corrente, A. M., Macdonald, C. L. B. A simple route to phosphamethine cyanines from S,N-heterocyclic carbenes. Dalton Trans. 45 (5), 2138-2147 (2016).
- Pangborn, A. B., Ma Giardello, ., Grubbs, R. H., Rosen, R. K., Timmers, F. J. Safe and Convenient Procedure for Solvent Purification. Organometallics. 15 (5), 1518-1520 (1996).
- Smaliy, R. V., Beaupérin, M., et al. Hexaphosphine: A multifaceted ligand for transition metal coordination. Eur. J. Inorg. Chem. (9), 1347-1352 (2012).
- Klebach, T. C., Lourens, R., Bickelhaupt, F. Synthesis of mesityldiphenylmethylenephosphine: a stable compound with a localized phosphorus:carbon bond. J. Amer. Chem. Soc. 100 (15), 4886-4888 (1978).
- Alcarazo, M. α-Cationic Phosphines: Synthesis and Applications. Chem. Eur. J. 20 (26), 7868-7877 (2014).
