Expanding the Family of Uranium(III) Alkyls: Synthesis and Characterization of Mixed‐Ligand Derivatives. Issue 15 (20th January 2016)

• Record Type: Journal Article
• Authors: Matson, Ellen M.; Kiernicki, John J.; Fanwick, Phillip E.; Bart, Suzanne C.
• Other Names: Pettinari C. guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 15/16(2016)
• Page Start: 2527
• Page End: 2533
• Publication Date: 2016-01-20
• Subjects: Actinides -- Uranium -- Tridentate ligands -- Alkylation -- Cyclopentadienyl ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501251
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The generation of uranium(III) alkyls supported by hydrotris(pyrazolyl)borate (Tp) and pentamethylcyclopentadienyl (Cp*) ligands is reported. Mixed ancillary ligand frameworks were synthesized by treating TpUI2 (THF)3 (1 ) and Cp*UI2 (THF)3 with potassium hydrotris(pyrazolyl)borate salts. Addition of one equivalent of potassium hydrotris(3, 5‐dimethylpyrazolyl)borate (Tp*) generated TpTp*UI (2 ), while treatment of Cp*UI2 (THF)3 with either KTp or KTp* resulted in the respective formation of Cp*TpUI(THF) (3 ) or Cp*Tp*UI(THF) (4 ). Alkylation of2 with KCH2 Ph or NaCH2 SiMe3 furnished TpTp*UCH2 Ph (2 ‐CH2 Ph) or TpTp*UCH2 SiMe3 (2 ‐CH2 SiMe3 ). Similarly, treatment of3 with NaCH2 SiMe3 formed Cp*TpUCH2 SiMe3 (3 ‐CH2 SiMe3 ), whereas treatment of4 with KCH2 Ph generated Cp*Tp*UCH2 Ph (4 ‐CH2 Ph). All compounds were characterized by multinuclear NMR, IR, and electronic absorption spectroscopy. Compounds2 ‐CH2 Ph, 3, and3 ‐CH2 SiMe3 were structurally characterized using X‐ray crystallography as well. Abstract : The generation of uranium(III) monoiodide and alkyls supported by both hydrotris(pyrazolyl)borate (Tp) and pentamethylcyclopentadienyl (Cp*) ligands is reported.