Year: 2023
Type: article
Abstract: Uranium diazomethanediide complexes can be prepared and their synthesis, structure and reactivity were explored. Reaction of the uranium imido compound [ η 5 ‐1,2,4‐(Me 3 Si) 3 C 5 H 2 ] 2 U=N( p ‐tolyl)(dmap) ( 1 ) or [ η 5 ‐1,3‐(Me 3 C) 2 C 5 H 3 ] 2 U=N( p ‐tolyl)(dmap) ( 4 ) with Me 3 SiCHN 2 cleanly yields the first isocyanoimido metal complexes [ η 5 ‐1,2,4‐(Me 3 Si) 3 C 5 H 2 ] 2 U(=NNC)( μ ‐CNN=)U(dmap)[ η 5 ‐1,2,4‐(Me 3 Si) 3 C 5 H 2 ] 2 ( 2 ) and {[ η 5 ‐1,3‐(Me 3 C) 2 C 5 H 3 ] 2 U[ μ ‐(=NNC)]} 6 ( 5 ), respectively. Both compounds exhibit remarkable thermal stability and were fully characterized. According to density functional theory (DFT) studies the bonding between the Cp 2 U 2+ and [NNC] 2− moieties is strongly polarized with a significant 5 f orbital contribution, which is also reflected in the reactivity of these complexes. For example, complex 5 acts as a nucleophile toward alkylsilyl halides and engages in a [2+2] cycloaddition with CS 2 , but no reaction occurs in the presence of internal alkynes.
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,250
Awards: G2933745529, G7009667666
OpenAlex ID: W4387965547