Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. C-H Bond Activation by an Isolated Dinuclear U(III)/U(IV) Nitride
 
research article

C-H Bond Activation by an Isolated Dinuclear U(III)/U(IV) Nitride

Palumbo, Chad T.  
•
Scopelliti, Rosario  
•
Zivkovic, Ivica  
Show more
February 12, 2020
Journal Of The American Chemical Society

Synthetic studies of bimetallic uranium nitride complexes with the N(SiMe3)(2) ligand have generated a new nitride complex of U(III), which is highly reactive toward C-H bonds and H-2. Treatment of the previously reported U(IV)/U(IV) nitride complex [Na(DME)(3)][((Me3Si)(2)N)(2)U(mu-N)(mu-kappa(2):CN-CH2SiMe2NSiMe3)U(N(SiMe3)(2))(2)] (DME = 1,2-dimethoxyethane), 1, with 2 equiv of HNEt3BPh3 yielded the cationic U(IV)/U(IV) nitride complex, [{((Me3Si)(2)N)(2)U(THF)}(2)(mu-N)][BPh4] (THF = tetrahydrofuran), 3, by successive protonolysis of one N(SiMe3)(2) ligand and the uranium-methylene bond. Reduction of 3 with KC8 afforded a rare example of a U(III) nitride, namely, the U(III)/U(IV) complex, [{((Me3Si2N)(2)U(THF)}(2)(mu-N)], 4. Complex 4 is highly reactive and undergoes 1,2-addition of the C-H bond of the N(SiMe3)(2) ligand across the uranium-nitride moiety to give the U(III)/U(IV) inside cyclometalate complex, [{((Me3Si)(2)N)(2)(THF)U(mu-NH)(mu-kappa(2):C,N - CH2SiMe2NSiMe3)U(N(SiMe3)(2)))(THF)], 5. Complex 4 also reacts with toluene at -80 degrees C to yield an inverse sandwich imide complex arising from C-H bond activation of toluene, [{((Me3SO2N)(2)U(THF)}(2)(mu-N)]{((Me3SO2N)(3)U(mu-NH)U(N(SiMe3)(2))(C7H8)], 6. Complex 4 effects the heterolytic cleavage of the C-H of phenylacetylene to yield the imide acetylide [{((Me3Si)(2)N)(2)U(THF)[(2)(mu-N)][((Me3Si)(2)N)(2)U(eta(1)-CCPh)(mu(2)-NH)(mu(2)-eta(2): eta(1)-CCPh)U(N(SiMe3)(2))(2)], 7. Complex 4 also reacts with H-2 to produce an imide hydride U(III)/U(IV) complex, [{((Me3SO2N)(2)U(THF)}(2)(mu-NH)(mu-H)], 9. These data demonstrate that nitride complexes of U(III) are accessible with amide ligands and show the high reactivity of molecular U(III) nitrides in C-H bond activation.

  • Files
  • Details
  • Metrics
Loading...
Thumbnail Image
Name

Palumbojacs.9b12804acceptedmanuscript.pdf

Type

Postprint

Version

Accepted version

Access type

openaccess

License Condition

Copyright

Size

2.44 MB

Format

Adobe PDF

Checksum (MD5)

6f1f44dcad2df3ec01761d7dcf790aa8

Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés