10.1021/om200612h.s005
Ellen M. Matson
Ellen M.
Matson
Phillip E. Fanwick
Phillip E.
Fanwick
Suzanne C. Bart
Suzanne C.
Bart
Formation of Trivalent U–C, U–N, and U–S Bonds and Their Reactivity toward Carbon Dioxide and Acetone
American Chemical Society
2011
SPh
2Ph
Full characterization
carbon dioxide results
isolable yields
NHCH
OC
bond
CCPh
1 H NMR
carbamate moiety
AcetoneA family
2CNHCH
trimethylsilyl halides
1 atm
CH
CO
Tp
Reversible insertion
benzyl ligand
trivalent uranium acetylides
IR spectroscopies
Carbon Dioxide
2011-11-14 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Formation_of_Trivalent_U_C_U_N_and_U_S_Bonds_and_Their_Reactivity_toward_Carbon_Dioxide_and_Acetone/2585470
A family of uranium(III) complexes of the form Tp*<sub>2</sub>UX (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, X = CCPh (<b>2-CCPh</b>), CCSiMe<sub>3</sub> (<b>3-CCSiMe</b><sub><b>3</b></sub>), NHPh (<b>4-NHPh</b>), NHCH<sub>2</sub>Ph (<b>5-NHCH</b><sub><b>2</b></sub><b>Ph</b>), SPh (<b>6-SPh</b>)) have been synthesized in quantitative yields by protonation of the benzyl group Tp*<sub>2</sub>U(CH<sub>2</sub>Ph) (<b>1-CH</b><sub><b>2</b></sub><b>Ph</b>) with organic precursors. Full characterization of these complexes, which contain newly formed uranium–carbon, uranium–nitrogen, and uranium–sulfur bonds, was performed using <sup>1</sup>H NMR and IR spectroscopies. These data along with the structural parameters of the uranium acetylide (<b>2-CCPh</b>) and uranium thiolate (<b>6-SPh</b>) species are reported. Treating the trivalent uranium acetylides and amides with 1 atm of carbon dioxide results in its insertion into the uranium–element bond to form the corresponding carboxylate or carbamate moiety in quantitative isolable yields. Reversible insertion of carbon dioxide (1 atm) into the uranium–sulfur bond of Tp*<sub>2</sub>U(SPh) (<b>6-SPh</b>) was also noted. The new family of CO<sub>2</sub>-inserted uranium(III) derivatives Tp*<sub>2</sub>UO<sub>2</sub>CX (X = CCPh (<b>7-O</b><sub><b>2</b></sub><b>CCCPh</b>), CCSiMe<sub>3</sub> (<b>8-O</b><sub><b>2</b></sub><b>CCCSiMe</b><sub><b>3</b></sub>), NHPh (<b>9-O</b><sub><b>2</b></sub><b>CNHPh</b>), NHCH<sub>2</sub>Ph (<b>10-O</b><sub><b>2</b></sub><b>CNHCH</b><sub><b>2</b></sub><b>Ph</b>), SPh (<b>11-O</b><sub><b>2</b></sub><b>CSPh</b>)) has been characterized spectroscopically and, in the case of <b>7-O</b><sub><b>2</b></sub><b>CCCPh</b>, crystallographically. The newly formed U–O bonds were cleaved by addition of trimethylsilyl halides, generating the monohalide derivative. Attempts to insert acetone into the uranium–carbon bonds of <b>1-CH</b><sub><b>2</b></sub><b>Ph</b> and <b>2-CCPh</b> or the uranium–nitrogen bond in <b>4-NHPh</b> resulted exclusively in protonation of the benzyl ligand and isomerization to form a rare enolate complex Tp*<sub>2</sub>U(OC(CH<sub>3</sub>)CH<sub>2</sub>) (<b>12-OC(CH</b><sub><b>3</b></sub><b>)CH</b><sub><b>2</b></sub>). This complex has been fully characterized by <sup>1</sup>H NMR and infrared spectroscopies as well as X-ray crystallography.