Access to Extended Polyphosphorus Frameworks
Access to Extended Polyphosphorus Frameworks
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DOI：
10.1002/anie.201001000
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Scheer, Manfred
中科院分区：
文献类型：
--
作者：
Dielmann, Fabian;Sierka, Marek;Scheer, Manfred
P4的活化是化学中的一个当前主题。最近，主族元素产生了很大的影响，它们能够打开一个，[1]两个，[2]或三个P2P键[3]，并且可以将P4部分降解为P2或P1单元。[4]P4通过N-杂环卡宾（NHC）的聚集也表明可以实现A中的大P12单元。[5]此外，更大的阳离子Pn+（n 89）[6]和阴离子Pn <$（n 49）[6，7]聚磷物种已在气相中使用激光烧蚀技术产生。Baudler及其同事在有机溶剂中的早期研究导致了大量有机取代的聚磷化合物。[8]他们还实现了较大聚磷化物的混合物的合成，如P16 2 H，P19 3 H和P21 3 H。[9]这些结构中的一些被部分分离和结构表征[10]，如聚磷化物P26 4 π。[11]与主族化合物和元素对P4的活化相反，[12]过渡金属化合物对P4的活化是一个已建立的领域[13]，并且在开发有机磷化合物的合成工艺方面具有很高的兴趣，这些工艺绕过了PCl 3作为关键前体。迄今为止，所发现的最大中性Pn物种是[{（Bu 3 P）2Ni} 4P 14]（B），其是由两个P7单元从Li 3 P7· 3 DME开始缩合而合成的。[14]使用P4作为起始材料，最大的结构表征的中性Pn配体络合物是[{CpCr（CO）2} 5（P10）][15]和[（CpRM）4P 10]（M= Rh，CpR= Cp ''= η5-1，3-tBu 2C 5 H3;[16] M= Co，CpR= CpSi= η5-1，3-（SiMe 3）2C 5 H3）[17]（C）。C的结构是两个环P5单元的缩合产物。从P_4中得到的最大Pn配合物为[（Cp ″ Co）_3P_12]。（D; Cp“”= η5-1，2，4-tBu3C5H2），其通过31 PNMR光谱鉴定，并由谢勒和同事在1908下在[Cp“"Co（CO）2]与P4共热之后作为次要产物（3%）或以中等产率（23%）获得。在室温下通过光解，然后通过[（Cp“"Co）3 P8]（10%）。[18]此外，在这两个反应中，[（Cp“"Co）2（P2）2]在热分解中作为主要产物（22%）而在光解中作为次要产物（4%）形成。目前的知识水平提出了一个问题，即是否有合理的方法来合成更大的中性Pn聚集体，以模拟P4向Hittorf磷的转化，[19]或其他多磷结构，这些结构被计算为比P4磷更稳定。[20]由于这个原因，使用能够消耗P4四面体并将它们联合收割机组合成更大种类的不饱和复合物片段似乎是有利的。由于显然CpRCo部分在大Pn单元的稳定中起重要作用，因此想到了[（Cp“"Co）2（η4：η4-C7 H8）]（1）[21]的使用。配合物1在溶液中部分解离，释放出电子不饱和的14价电子[Cp“"Co]片段。[21]这些高反应性金属/配体片段然后可以在非常温和的条件下与P4反应，与[Cp“"Co（CO）2]与P4的相当低的反应性形成对比。[22]在这里，我们介绍了使用这种不饱和配合物根据反应程序的类型和温度选择性地形成产物。这些受控反应可用于获得最大的结构表征的含有P16和P24单元的聚磷络合物。
The activation of P4 is an current topic in chemistry. Recently, a big impact was made by main-group elements that are able to open one,[1] two,[2] or three PÀP bonds [3] and can degrade the P4 moiety to a P2 or P1 unit.[4] Aggregation of P4 by N-heterocyclic carbenes (NHCs) has also shown that the large P12 unit in A can be achieved.[5] Moreover, larger cationic Pn+(n 89)[6] and anionic Pn À (n 49)[6, 7] polyphosphorus species have been generated in the gas phase using laser ablation techniques. Earlier investigations in organic solvents by Baudler and co-workers led to a large number of organosubstituted polyphosphorus compounds.[8] They have also achieved the synthesis of mixtures of the larger polyphosphides, such as P16 2À, P19 3À, and P21 3À.[9] Some of these structures were partially isolated and structurally characterized [10] as was the polyphosphide P26 4À.[11] In contrast to this activation of P4 with main-group compounds and elements,[12] the activation of P4 by transitionmetal compounds is an established field [13] and of high interest regarding the development of processes for the synthesis of organophosphorus compounds that circumvent PCl3 as a key precursor. To date, the largest neutral Pn species found is [{(Bu3P) 2Ni} 4P14](B), which was synthesized by the condensation of two P7 units starting from Li3P7· 3 DME.[14] Using P4 as starting material, the largest structurally characterized neutral Pn ligand complexes are [{CpCr (CO) 2} 5 (P10)][15] and [(CpRM) 4P10](M= Rh, CpR= Cp’’= η5-1, 3-tBu2C5H3;[16] M= Co, CpR= CpSi= η5-1, 3-(SiMe3) 2C5H3)[17](C). The structure of C is reminicent of the condensation of two cyclo-P5 units. The largest Pn complex obtained from P4 to date is [(Cp’’’Co) 3P12](D; Cp’’’= η5-1, 2, 4-tBu3C5H2), which was identified by 31PNMR spectroscopy and obtained by Scherer and coworkers as a minor product (3%) after the co-thermolysis of [Cp’’’Co (CO) 2] with P4 at 1908 or in moderate yields (23%) by photolysis at room temperature followed by [(Cp’’’Co) 3P8](10%).[18] Furthermore, in both reactions,[(Cp’’’Co) 2 (P2) 2] was formed in the thermolysis as major (22%) and in the photolysis as the minor product (4%). The current level of knowledge raised the question as to whether there are rational ways to synthesize larger neutral Pn aggregates to mimic the transformation of P4 to Hittorf s phosphorus,[19] or other polyphosphorus structures, which are calculated to be more stable than P4 phosphorus.[20] For this reason, the use of an unsaturated complex fragment that is able to consume P4 tetrahedra and combine these to larger species seemed to be advantageous. As it is obvious that CpRCo moieties play an important role in the stabilization of large Pn units, the use of [(Cp’’’Co) 2 (η4: η4-C7H8)](1)[21] came to mind. Complex 1 partly dissociates in solution to liberate electronically unsaturated 14-valence-electron [Cp’’’Co] fragments.[21] These highly reactive metal/ligand fragments could then react with P4 under very mild conditions, in contrast to the rather low reactivity of [Cp’’’Co (CO) 2] with P4.[22] Herein we present the use of this unsaturated complex to form products selectively, depending on the type of reaction procedure and the temperature. These controlled reactions can be used to achieve the largest structurally characterized polyphosphorus complexes containing P16 and P24 units.