Facile synthetic methods for the diversification of catena-polyphosphorus cations
Facile synthetic methods for the diversification of catena-polyphosphorus cations
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DOI：
10.1002/anie.200462997
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Decken, A
中科院分区：
文献类型：
--
作者：
Burford, N;Dyker, CA;Decken, A
磷形成链状化合物的倾向由大量结构特征的聚膦[1，2]和所报道的均多原子阴离子证明。[3]相比之下，全面表征的多磷阳离子限于膦基鏻 1、[4-9]膦基二鏻 2、[10]二膦基二鏻 3、[11]和膦基二鏻 4 [12，13]离子（方案1）。然而，阳离子5、[7，14] 6、[15] 7、[8，14，16]和8 [17]的最近和独特的例子说明了多样化的潜力，并强调了链状多磷阳离子作为磷化学中未充分探索的途径。在这种情况下，我们已经利用了简易的反应的聚膦（二，四，五物种），以制备一系列新的有机取代的二膦基膦9和环四膦基膦阳离子10。四甲基二膦或四苯基二膦与Me 2 PCl或Ph 2 PCl在Me 3SiOSO 2CF 3（TMSOTf）存在下的反应混合物的31 P NMR光谱[18]显示了相应的有机取代的链状-二膦膦鎓阳离子9a、9 b、9 c和9 f的快速、定量形成（方案2）。9的衍生物可以设想为膦刘易斯受体上的二膦配体（类似于1，因此代表R 0上R3 P的络合物
The propensity for phosphorus to form catenated compounds is evidenced by the extensive arrays of structurally characterized polyphosphines [1, 2] and homopolyatomic anions reported.[3] In contrast, comprehensively characterized polyphosphorus cations are limited to phosphinophosphonium 1,[4–9] phosphinodiphosphonium 2,[10] diphosphiranodiphosphonium 3,[11] and phosphidodiphosphonium 4 [12, 13] ions (Scheme1). Nevertheless, recent and unique examples of cations 5,[7, 14] 6,[15] 7,[8, 14, 16] and 8 [17] illustrate the potential for diversification and highlight catena-polyphosphorus cations as an underexplored avenue in phosphorus chemistry. In this context, we have exploited facile reactions of polyphosphines (di, tetra, and penta species) to prepare a series of new organosubstituted diphosphinophosphonium 9 and cyclotetraphosphinophosphonium cations 10. The 31P NMR spectra for reaction mixtures of tetramethyldiphosphane or tetraphenyldiphosphane with Me2PCl or Ph2PCl in the presence of Me3SiOSO2CF3 (TMSOTf)[18] show rapid, quantitative formation of the corresponding organosubstituted catena-diphosphanophosphonium cations 9a, 9b, 9c, and 9 f (Scheme 2). Derivatives of 9 can be envisaged as diphosphine ligands on phosphenium Lewis acceptors (analogous to 1, thus representing complexes of R3P on R0