A Genuine Stannylone with a Monoatomic Two-Coordinate Tin(0) Atom Supported by a Bis(silylene) Ligand

Authors: 
Jian Xu, Chenshu Dai, Shenglai Yao, Jun Zhu, Matthias Driess
Journal: 
Angew. Chem. Int. Ed.
Year: 
2022
Volume: 
61
FirstPage-LastPage: 
e202114073
Keywords: 
TOC: 
Abstract: 

The monoatomic zero-valent tin complex (stannylone) {[Si II (Xant)Si II ]Sn 0 } 5 stabilized by a bis(silylene)xanthene ligand, [Si II (Xant)Si II = PhC(N t Bu) 2 Si(Xant)Si(N t Bu) 2 CPh], and its bis-tetracarbonyliron complex {[Si II (Xant)Si II ]Sn 0 [Fe(CO) 4 ] 2 } 4 are reported. The stannylone 5 bearing a two-coordinate zero-valent tin atom is synthesized by reduction of the precursor 4 with potassium graphite. Compound 4 results from the Sn II halide precursor {[Si II (Xant)Si II ]Sn II Cl}Cl 2 or {[Si II (Xant)Si II ]SnBr 2 } 3 through reductive salt-metathesis reaction with K 2 Fe(CO) 4 . According to density functional theory (DFT) calculations, the highest occupied molecular orbital (HOMO) and HOMO-1 of 5 correspond to a π-type lone pair with delocalization into both adjacent vacant orbitals of the Si II atoms and a σ-type lone pair at the Sn 0 center, respectively, indicating genuine stannylone character.

https://onlinelibrary.wiley.com/doi/10.1002/anie.202114073

Doi: 
10.1002/anie.202114073