Electronic properties of polyoxometalate derivatives [(C₂B₉H₁₁) M'M₅O₁₈]^n‐ (M' = Ti^IV, Mo^VI, W^VI; M = Mo^VI, W^VI): Protonation, Electronic Spectra, and Redox Properties

Abstract

Density functional theory is used to study the electronic structures and properties of Lindqvist‐type polyoxometalates‐supported organometallic compounds [LM'M 5 O 18 ] n– (L = [C 2 B 9 H 11 ] 2– (Cb), [C 5 H 5 ] – (Cp); M' = Ti IV , Mo VI , W VI ; M = Mo VI , W VI ). [(Cb)M'M 5 O 18 ] n– are a series of novel compounds designed in this work, based on related experiment. The calculated results reveal that the Cb ligand is able to form a σ , 2 π triple bond with M', which is similar to the bond character in [(Cp)M'M 5 O 18 ] n– . However, comparing with the protonation, electronic spectra and redox properties of [(Cp)M'M 5 O 18 ] n– and [M'M 5 O 19 ] n– , [(Cb)M'M 5 O 18 ] n– species show the advantageous electronic properties owning to the superior electron donating ability of the Cb ligand. © 2015 Wiley Periodicals, Inc.