1223505-56-3Relevant articles and documents
Terphenyl substituted derivatives of manganese(II): Distorted geometries and resistance to elimination
Ni, Chengbao,Fettinger, James C.,Long, Gary J.,Power, Philip P.
, p. 10664 - 10670 (2011/01/09)
Reaction of {Li(THF)Ar′MnI2}2 (Ar′ = C6H3-2,6-(C6H2-2,6- iPr3)2) with LiAr′, LiCCR (R = tBu or Ph), or (C6H2-2,4,6-iPr 3)MgBr(THF)2 afforded the diaryl MnAr′2 (1), the alkynyl salts Ar′Mn(CCtBu)4{Li(THF)} 3 (2) and Ar′Mn(CCPh)3Li3(THF)(Et 2O)2(μ3-I) (3), and the manganate salt {Li(THF)}Ar′Mn(μ-I)(C6H2-2,4,6- iPr3) (4), respectively. Complex 4 reacted with one equivalent of (C6H2-2,4,6-iPr 3)MgBr(THF)2 to afford the homoleptic dimer {Mn(C 6H2-2,4,6-iPr3)(μ-C 6H2-2,4,6-iPr3)}2 (5), which resulted from the displacement of the bulkier Ar′ ligand in preference to the halogen. The reaction of the more crowded {Li(THF) Ar*MnI2}2 (Ar* = C6H 3-2,6-(C6H2-2,4,6-iPr 3)2) with LitBu gave complex Ar*Mn tBu (6). Complex 1 is a rare monomeric homoleptic two-coordinate diaryl Mn(ii) complex; while 6 displays no tendency to eliminate β-hydrogens from the tBu group because of the stabilization supplied by Ar*. Compounds 2 and 3 have cubane frameworks, which are constructed from a manganese, three carbons from three acetylide ligands, three lithiums, each coordinated by a donor, plus either a carbon from a further acetylide ligand (2) or an iodide (3). The Mn(ii) atom in 4 has an unusual distorted T-shaped geometry while the dimeric 5 features trigonal planar manganese coordination. The chloride substituted complex Li2(THF) 3{Ar′MnCl2}2 (7), which has a structure very similar to that of {Li(THF)Ar′MnI2}2, was also prepared for use as a possible starting material. However, its generally lower solubility rendered it less useful than the iodo salt. Complexes 1-7 were characterized by X-ray crystallography and UV-vis spectroscopy. Magnetic studies of 2-4 and 6 showed that they have 3d5 high-spin configurations. The Royal Society of Chemistry 2010.
