Synthesis and structures of doubly-bridged dicyclopentadienyl dinuclear rhenium complexes, and their photochemical reactions with aromatic halides in benzene
Zhu, B; Huang, X; Hao, X
| HERO ID | 2896770 |
|---|---|
| In Press | No |
| Year | 2014 |
| Title | Synthesis and structures of doubly-bridged dicyclopentadienyl dinuclear rhenium complexes, and their photochemical reactions with aromatic halides in benzene |
| Authors | Zhu, B; Huang, X; Hao, X |
| Journal | Dalton Transactions |
| Volume | 43 |
| Issue | 44 |
| Page Numbers | 16726-16736 |
| Abstract | Reaction of the doubly-bridged biscyclopentadienes (C5H4(EMe2))(C5H4(SiMe2)) (E = Si(1a), or C(1b)) with Re-2(CO)(10) in refluxing mesitylene gave the corresponding dirhenium carbonyl complexes [(eta(5)-C5H3)(2)(EMe2)(SiMe2)][Re(CO)(3)](2) (trans-2a, b and cis-2a, b), and the desilylated products [(eta(5)-C5H4)(2)(EMe2)][Re(CO)(3)](2) (3a, b). Photolysis of trans-2a, b with a series of aryl halides in benzene results in the formation of biphenyl, together with the corresponding rhenium dihalide complexes trans-[(eta(5)-C5H3)(2)(EMe2)(SiMe2)][Re(CO)(3)][Re(CO)(2)X-2] (X = Cl, Br, I) (4, 6, 8, or 10) and trans-[(eta(5)-C5H3)(2)(EMe2)(SiMe2)][Re(CO)(2)X-2](2) (5, 7, or 9). Additional experiments indicate that one phenyl ring in the resulting biphenyl comes from aryl halides and the other phenyl ring comes from the solvent benzene. However, photolysis of trans-2a with benzyl chloride and n-hexyl chloride in benzene afforded the corresponding bibenzyl and n-dodecane, as well as the rhenium dichlorides 8 and 9. In addition, complex trans-2a can also activate the C-F bond on C6F6 to form the pentafluorophenyl rhenium fluoride trans-[(eta(5)-C5H3)(2)(SiMe2)(2)][Re(CO)(3)][Re(CO)(2)(C6F5)F] (11). Molecular structures of cis-2a, cis-2b, trans-2b, 3b, 6, 7, 8, 11, and 12 determined by X-ray diffraction are also presented. |
| Doi | 10.1039/c4dt02370f |
| Pmid | 25274024 |
| Wosid | WOS:000344250800023 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |