Understanding the Reactivity of Strained Sandwich Compounds with Aluminum or Gallium in Bridging Positions: Experiments and DFT Calculations

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• 作者：Bidraha Bagh ; Gabriele Schatte ; Jennifer C. Green ; Jens M眉ller
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：May 9, 2012
• 年：2012
• 卷：134
• 期：18
• 页码：7924-7936
• 全文大小：625K
• 年卷期：v.134,no.18(May 9, 2012)
• ISSN：1520-5126

文摘

The aluminum and gallium dichlorides (Mamx)ECl₂1a (E = Al; 82%) and 1b (E = Ga; 79%) (Mamx = 2,4-di-tert-butyl-6-[(dimethylamino)methyl]phenyl) reacted with dilithioferrocene or dilithioruthenocene to give [1]ferrocenophanes (2a, 2b) and [1]ruthenocenophanes (3a, 3b), respectively. The galla[1]ruthenocenophane 3b could be isolated from the reaction mixture through precipitation into hexane (50%), while 2a, 2b, and 3a underwent ring-opening polymerization under the reaction conditions of their formation reactions to give metallopolymers (M_w (DLS) between 8.07 and 106 kDa). Monomer 3b was polymerized using Karstedt鈥檚 catalyst resulting in an M_w of 28.6(卤6.3) kDa. In order to get an indication of the structure of polymers, bis(ferrocenyl) compounds (Mamx)EFc₂ (E = Al (4a), 51%; E = Ga (4b), 49%) were prepared and characterized by single crystal X-ray analysis. DFT calculations shed some light on the unexpected high reactivity of these new strained sandwich species. Optimized geometries of known aluminum and gallium-bridged [1]ferrocenophanes (Al(Pytsi) (6a), Ga(Pytsi) (6b); Pytsi = [dimethyl(2-pyridyl)silyl]bis(trimethylsilyl)methyl) and [1]ruthenocenophanes (Al(Me₂Ntsi) (7a), Ga(Me₂Ntsi) (7b); Me₂Ntsi = [(dimethylamino)dimethylsilyl]bis(trimethylsilyl)methyl) matched very well with experimental molecular structures. Geometries of species 2a, 2b, 3a, and 3b were optimized (BP86/TZ2P) and the structural influence of the tBu group of the Mamx ligand in ortho position was evaluated by optimizing molecular structures of the four unknown species where the ortho-tBu group was replaced by an H atom (2a^H, 2b^H, 3a^H, and 3b^H). The most pronounced structural effect was seen as a change of the orientation of the bridging moiety with respect to the sandwich unit. As the tBu group was removed, the aromatic ligand moved toward the freed-up space. The energetics (螖E, 螖H^298K, and 螖G^298K) accompanied by the structural changes were evaluated by a hydrogenolysis reaction of strained species resulting in Cp₂M (M = Fe, Ru) and respective aluminum and gallium dihydrides. This nonisodesmic reaction showed that [1]metallocenophanes equipped with the ortho-tBu group were on average 5.5 kcal/mol higher strained (螖H^298K) than species where the tBu group was lacking. The investigation of the isodesmic reaction between strained species and Cp₂M yielding bis(metallocenyl) compounds revealed that the ortho-tBu group sterically interacts with one of the metallocenyl units. The bis(metallocenyl) compounds are model compounds for the respective metallopolymers and one can conclude that even though the ortho-tBu group imposes additional strain on the starting metallocenophanes, this effect cancels out in ROPs because the ortho-tBu group imposes a similar strain on the resulting polymers. The uncovered steric repulsion between the ortho-tBu group and the sandwich moieties probably causes the ortho-tBu to act as an unusually sensitive NMR probe of the tacticity of the polymers.