Decken Andreas, Nikiforov Grigori B, Passmore Jack
Chemistry Department, University of New Brunswick, E3B 6E2, Fredericton, N.B., Canada.
Dalton Trans. 2006 Sep 28(36):4328-34. doi: 10.1039/b606012a. Epub 2006 Jul 6.
Reaction of TiF4 and LiORf (Rf = C(CF3)2Ph) in the donor solvent-THF lead to the isolation of the heterometallic lithium-titanium complex (THF)2Li(mu-F)2Ti(ORf)2(mu-F)2Ti(ORf)(2)(mu-F)2Li(THF)2 (1) and Ti(ORf)4 alkoxide (2). Interaction of TiF4 and LiORf in the non-coordinating and low polar toluene yielded only Ti(ORf)4 (2). Compounds 1 and 2 were characterized by X-ray single-crystal analysis, IR, NMR and mass spectrometry. Compound 1 is a centrosymmetric fluorine bridged dimer and contains the Li(mu-F)2Ti(mu-F)2Ti(mu-F)2Li cage. Complex 2 containing four bulky ligands is monomeric. NMR evidence is presented that the TiF4 and LiORf in THF solution gave lithium-titanium heterometallic complexes containing Li-(mu-F)-Ti and the Ti-(mu-F)-Ti bonds.
在给体溶剂四氢呋喃(THF)中,四氟化钛(TiF4)与全氟芳氧基锂(LiORf,Rf = C(CF3)2Ph)反应,得到异金属锂 - 钛配合物(THF)2Li(μ - F)2Ti(ORf)2(μ - F)2Ti(ORf)2(μ - F)2Li(THF)2(1)和钛醇盐Ti(ORf)4(2)。在非配位且低极性的甲苯中,TiF4与LiORf相互作用仅生成Ti(ORf)4(2)。通过X射线单晶分析、红外光谱、核磁共振和质谱对化合物1和2进行了表征。化合物1是一个中心对称的氟桥联二聚体,包含Li(μ - F)2Ti(μ - F)2Ti(μ - F)2Li笼状结构。含有四个庞大配体的配合物2是单体。核磁共振证据表明,在THF溶液中,TiF4和LiORf生成了含有Li-(μ - F)-Ti和Ti-(μ - F)-Ti键的锂 - 钛异金属配合物。