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.

Activation of non-polar bonds by an electron-rich gallagermylene

“…10 a Moreover, gallagermylene 1 not only reacted with insertion of the germylene unit into one P–P bond, which is typically observed in reactions of tetrylenes with P 4 , but with additional 1,2-migration of the L(Cl)Ga substituent from the Ge to the P atom. The migration of the L(Cl)Ga substituent was also recently observed in the P–P bond activation of the P 5 ring in Cp*Fe(η 5 -P 5 ) upon reaction with L(Cl)Ga-SiL 5 , 11 whereas heavier analogue L(Cl)Ga-GeL 5 failed to activate Cp*Fe(η 5 -P 5 ), clearly demonstrating the higher reactivity of Cl-bridged gallagermylene 1 compared to L(Cl)Ga-GeL 5 .…”

“…9 f In addition, the reaction of L(Cl)Ga-SiL 5 with Cp*Fe(η 5 -Pn 5 ) (Pn = P, As) resulted in Pn–Pn and Si–Ga bond cleavage, which is caused by the insertion of the silylene into the cyclo -Pn 5 rings. 11…”

Applications of low-valent compounds with heavy group-14 elements

“…Treatment of [Cp*Fe(η 5 -P 5 )] with gallasilylene ( Si14 ) led to the formation of different isomers ( Si64 ). 84…”

“…Compound Ge18 was reacted with [Cp*Fe(η 5 -As 5 )] at room temperature for 2 days to isolate the iron-germylene complex ( Ge47 ) (Scheme 186). 84…”

“…Compound Ge18 was obtained in 85% yield and the Ge-Ga bond distance was 2.5514(10) Å. 84 Scheme 28 Synthesis of compound Si38.…”