Carbon Dioxide Insertion into Uranium‐Activated Dicarbonyl Complexes

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

“…The reportedh omogeneous catalytic systems mainly rely on the d-transition metal complexes. In recent years, to benefitf rom their ability to adopt multiple oxidation states and their reducibility at low oxidation states,r esearchers in this field have expandedtheir studies to the 5f elements, [22][23][24][25][26][27][28][29] amongw hich are the trivalenturanium complexes. [30][31][32][33][34] In trivalentu ranium complexes, the electron-richUatom is protected by bulky ligands [30,35] such as the hydrotris(3,5-dimethylpyrazolyl)-borate ligand (Tp*), which is ab ulky Lewis base, [36,37] and the complexese xist as salts.…”

“…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 …”

Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes

“…These observations are in agreement with tetravalent uranium centers with a non-magnetic 3 H 4 ground state. 58 , 98 , 99 An interesting feature to note, is the difference in the plot of χ M vs. T of 1-EH and 2-EH . While the mononuclear complexes 1-EH show temperature-independent paramagnetism (TIP) over a wide temperature range from 10 to 62 K (for 1-SH and 1-SeH ) and 101 K ( 1-TeH ), followed by a steady decrease of the molar susceptibility, this feature is slightly less pronounced in the dinuclear complexes 2-SH and 2-SeH (TIP below 50 K, see ESI † ) and shows a significant difference in 2-TeH (TIP below 55 K).…”

Insights into the Mechanism of Reaction of [(C5Me5)2SmII(thf)2] with CO2 and COS by DFT Studies

“…[2][3][4][5][6][7][8] CO 2 -mediated isocyanate and carbamate formations have also been observed by multiple bond metathesis, [9 ] as well as productive CÀC bond formations by CO 2 insertions to uranium complexes. [10][11] The reactivity of f-block-element complexes with COS and CS 2 has also been investigated experimentally. [8,[11][12][13][14][15] Several cases of the reactivity of a Sm II complex with CO 2 , CS 2 , or COS have been reported, for example, [(C 5 Me 5 ) 2 SmA C H T U N G T R E N N U N G (thf) 2 ] reductively coupled CO 2 in THF at room temperature to form the oxalate sandwich complex [{(C 5 Me 5 ) 2 Sm} 2 (m-h 2 :h 2 -O 2 CCO 2 )] in > 90 % yield.…”

“…Sm II and U III complexes have shown their ability to convert CO 2 into various products, such as oxos, oxalates, and carbonates 2–8. CO 2 ‐mediated isocyanate and carbamate formations have also been observed by multiple bond metathesis, [9 ] as well as productive CC bond formations by CO 2 insertions to uranium complexes 10–11. The reactivity of f‐block‐element complexes with COS and CS 2 has also been investigated experimentally 8.…”