Sun Xiaofei, Hinz Alexander, Schulz Stephan, Zimmermann Lisa, Scheer Manfred, Roesky Peter W
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 15 Karlsruhe 76131 Germany
Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), University of Duisburg-Essen Universitätsstraße 5-7 Essen 45117 Germany.
Chem Sci. 2023 Apr 17;14(18):4769-4776. doi: 10.1039/d3sc00806a. eCollection 2023 May 10.
Insertion and functionalization of gallasilylenes [LSi-Ga(Cl)L] (L = PhC(NBu); L = [{2,6-iPrCHNCMe}CH]) into the -E rings of [CpFe(-E)] (Cp = -CMe; E = P, As) are reported. Reactions of [CpFe(-E)] with gallasilylene result in E-E/Si-Ga bond cleavage and the insertion of the silylene in the -E rings. [(LSi-Ga(Cl)L){(-P)FeCp}], in which the Si atom binds to the bent -P ring, was identified as a reaction intermediate. The ring-expansion products are stable at room temperature, while isomerization occurred at higher temperature, and the silylene moiety further migrates to the Fe atom, forming the corresponding ring-construction isomers. Furthermore, reaction of [Cp*Fe(-As)] with the heavier gallagermylene [LGe-Ga(Cl)L] was also investigated. All the isolated complexes represent rare examples of mixed group 13/14 iron polypnictogenides, which could only be synthesized by taking advantage of the cooperativity of the gallatetrylenes featuring low-valent Si(ii) or Ge(ii) and Lewis acidic Ga(iii) units/entities.
报道了镓硅烯[LSi-Ga(Cl)L]（L = PhC(NBu)；L = [{2,6-iPrCHNCMe}CH]）插入到[CpFe(-E)]（Cp = -CMe；E = P，As）的-E环中并进行官能化。[CpFe(-E)]与镓硅烯的反应导致E-E/Si-Ga键断裂，并且硅烯插入到-E环中。[(LSi-Ga(Cl)L){(-P)FeCp}]，其中Si原子与弯曲的-P环结合，被鉴定为反应中间体。扩环产物在室温下稳定，而在较高温度下发生异构化，并且硅烯部分进一步迁移至Fe原子，形成相应的环构建异构体。此外，还研究了[Cp*Fe(-As)]与较重的镓锗烯[LGe-Ga(Cl)L]的反应。所有分离出的配合物均代表了罕见的13/14族混合铁多氮化物实例，这些化合物只能通过利用具有低价Si(ii)或Ge(ii)的三价镓和路易斯酸性Ga(iii)单元/实体的协同作用来合成。
