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An Alumanylyttrium Complex with an Absorption due to a Transition from the Al−Y Bond to an Unoccupied d‐Orbital
Author(s) -
Sugita Kengo,
Yamashita Makoto
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000752
Subject(s) - homo/lumo , crystallography , chemistry , atomic orbital , absorption spectroscopy , ligand (biochemistry) , absorption (acoustics) , molecular orbital , ion , electron , stereochemistry , materials science , molecule , physics , organic chemistry , composite material , biochemistry , receptor , quantum mechanics
The reaction between a dialkyl‐substituted alumanyl anion and [Y(CH 2 SiMe 3 ) 2 (thf) 3 ][BPh 4 ] resulted in the formation of (dialkylalumanyl)yttrium complex 2 , which exhibits the first 2‐center–2‐electron (2 c‐2 e) Al−Y bond. The 1 H and 13 C NMR spectra of 2 together with an X‐ray crystallographic analysis indicated a C 2 v symmetrical structure. DFT calculations on 2 revealed that its LUMO consists of overlapping 3 p‐ and 4 d‐orbitals of the Al and Y atoms, respectively, and that the HOMO–LUMO gap is narrow. The UV/Vis spectrum of 2 exhibited a visible absorption at 432 nm, which suggests that the strong σ‐donating and π‐accepting character of the three‐coordinate dialkylalumanyl ligand generates a colored d 0 ‐complex that does not contain any π‐electrons.