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Reductive silylation of a uranyl dibenzoylmethanate complex: an example of controlled uranyl oxo ligand cleavage
| Content Provider | Semantic Scholar |
|---|---|
| Author | Pedrick, Elizabeth A. Wu, Guang Kaltsoyannis, Nikolas Hayton, Trevor W. |
| Copyright Year | 2014 |
| Abstract | Reaction of UO2(dbm)2(THF) (dbm = OC(Ph)CHC(Ph)O) with 1 equiv. of R3SiH (R = Ph, Et), in the presence of B(C6F5)3, results in the formation of U(OB{C6F5}3)(OSiR3)(dbm)2(THF) (R = Ph, 1; Et, 2), which were isolated as red-orange crystalline solids in good yields. Interestingly, the addition of 1 equiv. of H(dbm) to 2 results in protonation of the –OSiEt3 ligand and formation of U(OB{C6F5}3)(dbm)3 (4) in 33% yield, along with formation of HOSiEt3. Furthermore, addition of HOSiEt3 and 1 equiv. of THF to 4, results in the formation 2, revealing that this process is reversible. The two-step conversion of UO2(dbm)2(THF) to 4 represents a rare example of controlled uranyl oxo ligand cleavage at ambient temperature and pressure. Comparison of diffraction and density functional theory data for 4 suggests the presence of the inverse trans influence, with a very shallow potential energy well for distortion along the trans U–O bond. |
| Starting Page | 3204 |
| Ending Page | 3213 |
| Page Count | 10 |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/C4SC00996G |
| Volume Number | 5 |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/sc/c4/c4sc00996g/c4sc00996g1.pdf |
| Alternate Webpage(s) | https://pubs.rsc.org/en/content/articlepdf/2014/sc/c4sc00996g |
| Alternate Webpage(s) | http://discovery.ucl.ac.uk/1437499/1/c4sc00996g.pdf |
| Alternate Webpage(s) | https://doi.org/10.1039/C4SC00996G |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
