Manganese(II) Alkyl/蟺-Allyl Complexes Resistant to Ligand Redistribution
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- 作者：Preeti Chadha ; David J. H. Emslie ; Hilary A. Jenkins
- 刊名：Organometallics
- 出版年：2014
- 出版时间：March 24, 2014
- 年：2014
- 卷：33
- 期：6
- 页码：1467-1474
- 全文大小：345K
- 年卷期：v.33,no.6(March 24, 2014)
- ISSN：1520-6041
文摘
The reaction of [Li(THF)4][(Mn{C(SiMe3)3})3(渭-Cl)4(THF)] (1) with K(allylTMS2) (allylTMS2 = 1,3-C3H3(SiMe3)2) afforded [(畏3-allylTMS2)Mn{C(SiMe3)3}{ClLi(THF)3}] (2). Attempted sublimation of 2 yielded [(畏3-allylTMS2)Mn{C(SiMe3)3}(THF)] (3), indicating that 2 extrudes LiCl at elevated temperatures. Additionally, LiCl in 2 was displaced by reaction with PMe3, quinuclidine, and dmap (dmap = 4-(dimethylamino)pyridine), providing [(畏3-allylTMS2)Mn{C(SiMe3)3}(L)] (L = PMe3 (4), quinuclidine (5), dmap (6)). Treatment of PMe3 complex 4 with BPh3 yielded bright red [(allylTMS2)Mn{C(SiMe3)3}] (7) accompanied by a precipitate of Ph3B(PMe3). Mixed alkyl/蟺-allyl manganese(II) complexes 2鈥?b>7 are pyrophoric red solids with a high-spin d5 configuration, and all were crystallographically characterized. In the solid-state structures, the allyl ligands in 2鈥?b>6 adopt a syn,syn configuration, whereas in base-free 7, the allyl ligand has a syn,anti configuration. Complexes 4, 5, and 7 sublimed cleanly (5 mTorr) at 70, 90, and 50 掳C, respectively. Complex 4 exhibited a particularly favorable combination of volatility and thermal stability, given that its appearance and powder X-ray diffraction pattern were unchanged after 24 h in a sealed flask at 100 掳C. Compounds 2鈥?b>7 are the first high-spin d5 mixed alkyl/allyl complexes, and 7 is the first room-temperature-stable example of a mononuclear transition-metal complex bearing only alkyl and allyl ligands.