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Substituted aromatic pentaphosphole ligands – a journey across the p-block
Chemical Science ( IF 7.6 ) Pub Date : 2021-09-14 , DOI: 10.1039/d1sc04296c Christoph Riesinger 1 , Gábor Balázs 1 , Michael Seidl 1 , Manfred Scheer 1
Chemical Science ( IF 7.6 ) Pub Date : 2021-09-14 , DOI: 10.1039/d1sc04296c Christoph Riesinger 1 , Gábor Balázs 1 , Michael Seidl 1 , Manfred Scheer 1
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The functionalization of pentaphosphaferrocene [Cp*Fe(η5-P5)] (1) with cationic group 13–17 electrophiles is shown to be a general synthetic strategy towards P–E bond formation of unprecedented diversity. The products of these reactions are dinuclear [{Cp*Fe}2{μ,η5:5-(P5)2EX2}][TEF] (EX2 = BBr2 (2), GaI2 (3), [TEF]− = [Al{OC(CF3)3}4]−) or mononuclear [Cp*Fe(η5-P5E)][X] (E = CH2Ph (4), CHPh2 (5), SiHPh2 (6), AsCy2 (7), SePh (9), TeMes (10), Cl (11), Br (12), I (13)) complexes of hetero-bis-pentaphosphole ((cyclo-P5)2R) or hetero-pentaphosphole ligands (cyclo-P5R), the aromatic all-phosphorus analogs of prototypical cyclopentadienes. Further, modifying the steric and electronic properties of the electrophile has a drastic impact on its reactivity and leads to the formation of [Cp*Fe(μ,η5:2-P5)SbICp′′′][TEF] (8) which possesses a triple-decker-like structure. X-ray crystallographic characterization reveals the slightly twisted conformation of the cyclo-P5R ligands in these compounds and multinuclear NMR spectroscopy confirms their integrity in solution. DFT calculations shed light on the bonding situation of these compounds and confirm the aromatic character of the pentaphosphole ligands on a journey across the p-block.
中文翻译：
取代芳香五磷配体——穿越 p 区的旅程
五磷杂二茂铁 [Cp*Fe(η 5 -P 5 )] ( 1 ) 与阳离子基团 13-17 亲电子试剂的官能化被证明是形成前所未有的多样性 P-E 键的通用合成策略。这些反应的产物是双核 [{Cp*Fe} 2 {μ,η 5:5 -(P 5 ) 2 EX 2 }][TEF] (EX 2 = BBr 2 ( 2 ), GaI 2 ( 3 ), [TEF] − = [Al{OC(CF 3 ) 3 } 4 ] − ) 或单核 [Cp*Fe(η 5 -P 5 E)][X] (E = CH 2 Ph ( 4 ), CHPh 2 ( 5 ), SiHPh 2 ( 6 ), AsCy 2 ( 7 ), SePh ( 9 ), TeMes ( 10 ), Cl ( 11 ), Br ( 12 ), I ( 13 ) ) 杂双五磷杂环磷配合物 ((环-P 5 ) 2 R)或杂五磷配体(环-P 5 R)，原型环戊二烯的芳香族全磷类似物。此外，改变亲电子试剂的空间和电子性质对其反应性产生巨大影响，并导致形成 [Cp*Fe(μ,η 5:2 -P 5 )SbICp'''][TEF] ( 8 )它具有三层结构。X 射线晶体学表征揭示了这些化合物中环-P 5 R 配体的轻微扭曲构象，多核 NMR 光谱证实了它们在溶液中的完整性。DFT 计算揭示了这些化合物的键合情况，并确认了五磷配体在穿过 p 块的过程中的芳香特征。
更新日期：2021-09-14
中文翻译：
取代芳香五磷配体——穿越 p 区的旅程
五磷杂二茂铁 [Cp*Fe(η 5 -P 5 )] ( 1 ) 与阳离子基团 13-17 亲电子试剂的官能化被证明是形成前所未有的多样性 P-E 键的通用合成策略。这些反应的产物是双核 [{Cp*Fe} 2 {μ,η 5:5 -(P 5 ) 2 EX 2 }][TEF] (EX 2 = BBr 2 ( 2 ), GaI 2 ( 3 ), [TEF] − = [Al{OC(CF 3 ) 3 } 4 ] − ) 或单核 [Cp*Fe(η 5 -P 5 E)][X] (E = CH 2 Ph ( 4 ), CHPh 2 ( 5 ), SiHPh 2 ( 6 ), AsCy 2 ( 7 ), SePh ( 9 ), TeMes ( 10 ), Cl ( 11 ), Br ( 12 ), I ( 13 ) ) 杂双五磷杂环磷配合物 ((环-P 5 ) 2 R)或杂五磷配体(环-P 5 R)，原型环戊二烯的芳香族全磷类似物。此外，改变亲电子试剂的空间和电子性质对其反应性产生巨大影响，并导致形成 [Cp*Fe(μ,η 5:2 -P 5 )SbICp'''][TEF] ( 8 )它具有三层结构。X 射线晶体学表征揭示了这些化合物中环-P 5 R 配体的轻微扭曲构象，多核 NMR 光谱证实了它们在溶液中的完整性。DFT 计算揭示了这些化合物的键合情况，并确认了五磷配体在穿过 p 块的过程中的芳香特征。
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