Issue 18, 2023

Snapshots of sequential polyphosphide rearrangement upon metallatetrylene addition

Abstract

Insertion and functionalization of gallasilylenes [LPhSi–Ga(Cl)LBDI] (LPh = PhC(NtBu)2; LBDI = [{2,6-iPr2C6H3NCMe}2CH]) into the cyclo-E5 rings of [Cp*Fe(η5-E5)] (Cp* = η5-C5Me5; E = P, As) are reported. Reactions of [Cp*Fe(η5-E5)] with gallasilylene result in E–E/Si–Ga bond cleavage and the insertion of the silylene in the cyclo-E5 rings. [(LPhSi-Ga(Cl)LBDI){(η4-P5)FeCp*}], in which the Si atom binds to the bent cyclo-P5 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(η5-As5)] with the heavier gallagermylene [LPhGe–Ga(Cl)LBDI] 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.

Graphical abstract: Snapshots of sequential polyphosphide rearrangement upon metallatetrylene addition

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Feb 2023
Accepted
30 Mar 2023
First published
17 Apr 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 4769-4776

Snapshots of sequential polyphosphide rearrangement upon metallatetrylene addition

X. Sun, A. Hinz, S. Schulz, L. Zimmermann, M. Scheer and P. W. Roesky, Chem. Sci., 2023, 14, 4769 DOI: 10.1039/D3SC00806A

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