Carbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes

Abstract

The reactions of f-block silylamido N-heterocyclic carbene (NHC) complexes ([M(L)(N{SiMe(3)}(2))(2)], M = Y, Ce, and U, L = bidentate alkoxy-tethered NHC ligand) with CO and CO(2) have been studied and compared to each other, to those of selected [M(L)(2)(N{SiMe(3)}(2))] complexes, and to those of [M(N{SiMe(3)}(2))(3)] to identify the effect of the labile NHC group on the small molecule activation chemistry. The small molecules COS and N(2)CPh(2) have also been studied.

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

“…[236] The selected [M(L) 2 (N{SiMe 3 } 2 )] and [M(N{SiMe 3 } 2 ) 3 ] complexes were also compared to identify the effect of the labile NHC group on small-molecule activation chemistry. [236] The selected [M(L) 2 (N{SiMe 3 } 2 )] and [M(N{SiMe 3 } 2 ) 3 ] complexes were also compared to identify the effect of the labile NHC group on small-molecule activation chemistry.…”

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

“…Addition of CO at ambient pressure and temperature to U(L)[N(SiMe 3 ) 2 ] 2 resulted in no reaction. However, heating the solution to 80 • C for 7 days afforded the pale brown U IV CO insertion product, U(L)[N(SiMe 3 ) 2 ][OC(CH 2 )SiMe 2 N(SiMe 3 )], which was isolated in 78% yield (Scheme 193) [11].…”

“…From this, dark brown and colorless single crystals of the ketimido complex U(L)[N(SiMe 3 ) 2 ] 2 (N CPh 2 ) and the amine H 2 NCHPh 2 , respectively, were grown (Scheme 194). However, they could not be separated by fractional crystallization [11].…”

“…As a result, the complexes Ln(L)[N(SiMe 3 ) 2 ] 2 all react rapidly to incorporate an equivalent of CO 2 , and affording trimethylsilyl isocyanate from silylamido ligand conversion (Scheme 14). However, the resultant rare-earth metal complexes could not be isolated due to loss of the carbene ligand and decomposition [11].…”

Computational Comparative Mechanistic Study of C−E (E=C,N,O,S) Coupling Reactions through CO2 Activation Mediated by Uranium(III) Complexes

“…The reported homogeneous catalytic systems mainly rely on the d ‐transition metal complexes . In recent years, to benefit from their ability to adopt multiple oxidation states and their reducibility at low oxidation states, researchers in this field have expanded their studies to the 5 f elements, among which are the trivalent uranium complexes …”