172275-47-7Relevant academic research and scientific papers
Reductive silylation of Cp?UO2(MesPDIMe) promoted by Lewis bases
Kiernicki,Harwood,Fanwick,Bart
, p. 3111 - 3119 (2016/02/20)
Functionalization of the uranyl moiety (UO22+) in Cp?UO2(MesPDIMe) (1-PDI) (MesPDIMe = 2,6-((Mes)NCMe)2C5H3N; Mes = 2,4,6-triphenylmethyl), which bears a reduced, monoanionic pyridine(diimine) ligand, is reported. Silylating reagents, R3Si-X (R = Me, X = Cl, I, OTf, SPh; R = Ph, X = Cl), effectively add across the strong OUO bonds in the presence of the Lewis base, OPPh3, generating products of the form (R3SiO)2UX2(OPPh3)2 (R = Me, X = I (2-OPPh3), Cl (3-OPPh3), SPh (5-OPPh3), OTf (6-OPPh3); R = Ph, X = Cl (4-OPPh3)). During this transformation, reduction to uranium(iv) occurs with loss of (Cp?)2 and MesPDIMe, each of which acts as a one-electron source. In the reaction, the Lewis base serves to activate the silyl halide, generating a more electrophilic silyl group, as determined by 29Si NMR spectroscopy, that undergoes facile transfer to the oxo groups. Complete U-O bond scission was accomplished by treating the uranium(iv) disiloxide compounds with additional silylating reagent, forming the family (Ph3PO)2UX4. All compounds were characterized by 1H NMR, infrared, and electronic absorption spectroscopies. X-ray crystallographic characterization was used to elucidate the structures of 2-OPPh3, 4-OPPh3, 5-OPPh3, and 6-OPPh3.
New Uranium Tetraiodide Complexes
Preez, Jan G. H. du,Zeelie, Ben
, p. 743 (2007/10/02)
A new type of uranium tetraiodide complex, viz.UI4L2 (where L = a bulky amide or phosphine oxide ligand) and new suitable starting materials for the preparation of uranium(IV) iodo-complexes have been prepared.
