Rottschäfer Dennis, Blomeyer Sebastian, Neumann Beate, Stammler Hans-Georg, Ghadwal Rajendra S
Molecular Inorganic Chemistry and Catalysis , Inorganic and Structural Chemistry , Center for Molecular Materials , Faculty of Chemistry , Universität Bielefeld , Universitätsstr. 25 , Bielefeld , D-33615 , Germany . Email:
Chem Sci. 2019 Oct 18;10(48):11078-11085. doi: 10.1039/c9sc04441h. eCollection 2019 Dec 28.
A series of unique CP-ring compounds [(ADC)P] (ADC = ArC{(DippN)C}; Dipp = 2,6-iPrCH; Ar = Ph , 3-MeCH , 4-MeCH , and 4-MeNCH ) are readily accessible in an almost quantitative yield by the direct functionalization of white phosphorus (P) with appropriate anionic dicarbenes [Li(ADC)]. The formation of 1,2,3-triphosphol-2-ides () suggests unprecedented [3 + 1] fragmentation of P into P and P. The P cation is trapped by the (ADC) to give , while the putative P anion reacts with additional P to yield the LiP species, a useful reagent in the synthesis of organophosphorus compounds. Remarkably, the P fragmentation is also viable with the related mesoionic carbenes (iMICs) (iMIC = ArC{(DippN)CCH}, i stands for imidazole-based) giving rise to . DFT calculations reveal that both the CN and CP-rings of are 6π-electron aromatic systems. The natural bonding orbital (NBO) analyses indicate that compounds are mesoionic species featuring a negatively polarized CP-ring. The HOMO-3 of is mainly the lone-pair at the central phosphorus atom that undergoes σ-bond formation with a variety of metal-electrophiles to yield complexes [{(ADC)P}M(CO) ] (M = Fe, = 4, Ar = Ph or 4-Me-CH ; M = Mo, = 5, Ar = Ph ; M = W, = 5, Ar = 4-MeNCH ).
一系列独特的环磷化合物[(ADC)P]（ADC = ArC{(DippN)C}；Dipp = 2,6 - 二异丙基苯基；Ar = 苯基、3 - 甲基苯基、4 - 甲基苯基和4 - 甲氨基苯基）可通过白磷（P）与适当的阴离子二卡宾[Li(ADC)]直接官能化以几乎定量的产率轻松获得。1,2,3 - 三磷杂环戊 - 2 - 亚基（）的形成表明P发生了前所未有的[3 + 1]断裂生成P 和P。P 阳离子被(ADC)捕获得到，而推测的P 阴离子与额外的P反应生成LiP物种，这是有机磷化合物合成中的一种有用试剂。值得注意的是，P断裂对于相关的中氮茚基卡宾（iMICs）（iMIC = ArC{(DippN)CCH}，i代表基于咪唑的）也是可行的，从而产生。密度泛函理论计算表明的CN环和CP环都是6π电子芳香体系。自然键轨道（NBO）分析表明化合物是具有负极化CP环的中氮茚物种。的HOMO - 3主要是中心磷原子上的孤对电子，它与各种金属亲电试剂形成σ键生成配合物[{(ADC)P}M(CO) ]（M = Fe， = 4，Ar = 苯基或4 - 甲基苯基；M = Mo， = 5，Ar = 苯基；M = W， = 5，Ar = 4 - 甲氨基苯基）。
