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Iodination of cyclo-E5 -Complexes (E=P, As).
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-05-28 , DOI: 10.1002/anie.202004812
Helena Brake 1 , Eugenia Peresypkina 1 , Alexander V Virovets 1 , Martin Piesch 1 , Werner Kremer 2 , Lisa Zimmermann 1 , Christian Klimas 1 , Manfred Scheer 1
Affiliation  

In a high‐yield one‐pot synthesis, the reactions of [Cp*M(η5‐P5)] (M=Fe (1), Ru (2)) with I2 resulted in the selective formation of [Cp*MP6I6]+ salts (3, 4). The products comprise unprecedented all‐cis tripodal triphosphino‐cyclotriphosphine ligands. The iodination of [Cp*Fe(η5‐As5)] (6) gave, in addition to [Fe(CH3CN)6]2+ salts of the rare [As6I8]2− (in 7) and [As4I14]2− (in 8) anions, the first di‐cationic Fe‐As triple decker complex [(Cp*Fe)2(μ,η5:5‐As5)][As6I8] (9). In contrast, the iodination of [Cp*Ru(η5‐As5)] (10) did not result in the full cleavage of the M−As bonds. Instead, a number of dinuclear complexes were obtained: [(Cp*Ru)2(μ,η5:5‐As5)][As6I8]0.5 (11) represents the first Ru‐As5 triple decker complex, thus completing the series of monocationic complexes [(CpRM)2(μ,η5:5‐E5)]+ (M=Fe, Ru; E=P, As). [(Cp*Ru)2As8I6] (12) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)2As4I4] (13) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck.

中文翻译:

环-E5-配合物的碘化(E = P,As)。

在高产量一锅合成,的反应的[Cp * M(η 5 -P 5)](M = Fe(上1),钌(2))与I 2导致[Cp的选择性形成* MP 66 ] +的盐(34)。产品包含前所未有的全顺式三脚架三膦-环三膦配体。的碘化的[Cp *的Fe(η 5 -As 5)](6)得到,除的[Fe(CH 3 CN)6 ] 2+稀土的盐[如68 ]2−(在7中)和[As 4 I 14 ] 2−(在8中)阴离子,是第一个阳离子型Fe-As三重复合物[(Cp * Fe)2(μ,η5 :5 -As 5) ] [As 6 I 8 ](9)。与此相反,碘化的[Cp *茹(η 5 -As 5)](10)没有导致的M-作为键的全切割。相反,获得了许多双核络合物:[(Cp * Ru)2(μ,η5 :5 -As 5)] [As 6 I 8 ] 0.511)表示第一个Ru-As 5三层复合物,从而完成了一系列单阳离子复合物[(Cp R M)2(μ,η5 :5- E 5)] +(M = Fe,Ru; E = P,As)。[(Cp * Ru)2 As 8 I 6 ](12)结晶为两种对映异构体的外消旋混合物,而[(Cp * Ru)2 As 4 I 4 ](13)结晶为对称和不对称异构体。 {AsI} in啶单元的独特四聚体作为中间甲板。
更新日期:2020-05-28
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