289620-17-3Relevant academic research and scientific papers
Manganese(II) Alkyl/π-Allyl complexes resistant to ligand redistribution
Chadha, Preeti,Emslie, David J. H.,Jenkins, Hilary A.
, p. 1467 - 1474 (2014)
The reaction of [Li(THF)4][(Mn{C(SiMe3) 3})3(μ-Cl)4(THF)] (1) with K(allyl TMS2) (allylTMS2 = 1,3-C3H 3(SiMe3)2) afforded [(η3- allylTMS2)Mn{C(SiMe3)3}{ClLi(THF)3}] (2). Attempted sublimation of 2 yielded [(η3-allyl TMS2)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 [(η3-allyl TMS2)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(SiMe 3)3}] (7) accompanied by a precipitate of Ph 3B(PMe3). Mixed alkyl/π-allyl manganese(II) complexes 2-7 are pyrophoric red solids with a high-spin d5 configuration, and all were crystallographically characterized. In the solid-state structures, the allyl ligands in 2-6 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 °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°C. Compounds 2-7 are the first high-spin d 5 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.
'Hemilabile' silyl pincer ligation: Platinum group PSiN complexes and triple C-H activation to form a (PSiC)Ru carbene complex
Ruddy, Adam J.,Mitton, Samuel J.,McDonald, Robert,Turculet, Laura
, p. 1159 - 1161 (2012/03/08)
The first example of PSiN mixed-donor silyl pincer ligation is described. Studies involving platinum group metal complexes of [(2-tBu 2PC6H4)(2-Me2NC6H 4)SiMe]- (tBu-PSiN-Me) confirmed that the ligand amino donor is labile. Within the coordination sphere of Ru, tBu-PSiN-Me is transformed into a PSiC ligand via multiple C-H bond activation events. The Royal Society of Chemistry 2012.
