Sun, Xiaofei and Hinz, Alexander and Schulz, Stephan and Zimmermann, Lisa and Scheer, Manfred and Roesky, Peter W. (2023) Snapshots of sequential polyphosphide rearrangement upon metallatetrylene addition. CHEMICAL SCIENCE, 14 (18). pp. 4769-4776. ISSN 2041-6520, 2041-6539
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Insertion and functionalization of gallasilylenes [(LSi)-Si-Ph-Ga(Cl)L-BDI] (L-Ph = PhC(NtBu)(2); L-BDI = [{2,6-iPr(2)C(6)H(3)NCMe}(2)CH]) into the cyclo-E-5 rings of [Cp*Fe(?(5)-E-5)] (Cp* = ?(5)-C5Me5; E = P, As) are reported. Reactions of [Cp*Fe(?(5)-E-5)] with gallasilylene result in E-E/Si-Ga bond cleavage and the insertion of the silylene in the cyclo-E-5 rings. [((LSi)-Si-Ph-Ga(Cl)L-BDI){(?(4)-P-5)FeCp*}], in which the Si atom binds to the bent cyclo-P-5 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(?(5)-As-5)] with the heavier gallagermylene [(LGe)-Ge-Ph-Ga(Cl)L-BDI] 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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | METAL; COMPLEXES; PENTAPHOSPHAFERROCENE; POLYARSENIDES; SILYLENE; LIGAND; CAGE; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 19 Mar 2024 14:42 |
| Last Modified: | 19 Mar 2024 14:42 |
| URI: | https://pred.uni-regensburg.de/id/eprint/60364 |
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