10.1021/ja509770t.s001
Bo Fang
Bo
Fang
Wenshan Ren
Wenshan
Ren
Guohua Hou
Guohua
Hou
Guofu Zi
Guofu
Zi
De-Cai Fang
De-Cai
Fang
Laurent Maron
Laurent
Maron
Marc D. Walter
Marc D.
Walter
An Actinide
Metallacyclopropene Complex: Synthesis,
Structure, Reactivity, and Computational Studies
American Chemical Society
2015
susceptibility data show
DFT studies complement
3C
potassium graphite
5 f orbitals
heterounsaturated molecules
Actinide Metallacyclopropene Complex
reactivity patterns
group 4 metals
KC
diazoalkane derivatives
Complex 2
actinide metallacyclopropene
Computational StudiesThe synthesis
2015-12-17 06:18:21
Journal contribution
https://acs.figshare.com/articles/journal_contribution/An_Actinide_Metallacyclopropene_Complex_Synthesis_Structure_Reactivity_and_Computational_Studies/2045277
The
synthesis, structure, and reactivity of an actinide metallacyclopropene
were comprehensively studied. The reduction of [η<sup>5</sup>-1,2,4-(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>]<sub>2</sub>ThCl<sub>2</sub> (<b>1</b>) with potassium graphite
(KC<sub>8</sub>) in the presence of diphenylacetylene (PhCCPh)
yields the first stable actinide metallacyclopropene [η<sup>5</sup>-1,2,4-(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>]<sub>2</sub>Th(η<sup>2</sup>-C<sub>2</sub>Ph<sub>2</sub>)
(<b>2</b>). The magnetic susceptibility data show that <b>2</b> is indeed a diamagnetic Th(IV) complex, and density functional
theory (DFT) studies suggest that the 5f orbitals contribute to the
bonding of the metallacyclopropene Th(η<sup>2</sup>-CC)
moiety. Complex <b>2</b> shows no reactivity toward alkynes,
but it reacts with a variety of heterounsaturated molecules such as
aldehyde, ketone, carbodiimide, nitrile, organic azide, and diazoalkane
derivatives. DFT studies complement the experimental observations
and provide additional insights. Furthermore, a comparison between
Th and group 4 metals reveals that Th<sup>4+</sup> shows unique reactivity
patterns.