Intramolecular Metal-Fluorocarbon Coordination, C-F Bond Activation and Lanthanoid-Fluoride Clusters with Tethered Polyfluorophenylamide Ligands
Intramolecular Metal-Fluorocarbon Coordination, C-F Bond Activation and Lanthanoid-Fluoride Clusters with Tethered Polyfluorophenylamide Ligands
复制标题
DOI：
10.1002/chem.200802294
复制
发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Wang, Jun
中科院分区：
文献类型：
--
作者：
Deacon, Glen B.;Forsyth, Craig M.;Wang, Jun
N，N-二乙基-或N，N-dimethyl-N‘-2，3，5，6-tetrafluorophenylethane-1，2-diamines(HL 1a，1b)分别与[M{N(SiMe3)(2)(2)}](M=Na，K)或[Yb{N(SiMe3)(2)}(2)(四氢呋喃)(2)]进行金属化反应，得到金属酰胺化合物[Na(L)(2a)，[K(L)](3a)和[Yb(L)(2)(四氢呋喃)(2)](4a，4b)。在N，N，N‘，N’-四甲基-1，2-乙二胺(TMEDA)存在下，Yb、Hg(C6F5)(2)和HL在THF或4a中与YbI2反应得到Yb配合物2a和3a分别得到[Na(L)(2)Na(TMeda)](5a)和[K-2(L)(2)(Tmeda)(2)](6a)，二甲醚的4a结晶得到[Yb(L)(2)(二甲醚)](7a)。它们的结构具有螯合金属酰胺和NR2给体以及额外的分子内M-F-C连接性，键长相对较短(Na-F 2.65-3.00埃；K-F 2.70-3.00埃；Yb-F 2.56埃)。Yb配合物在溶液中经过C-F活化，形成[Yb-4(L)(6)F-6](8a，8b)。X射线结构表明，[Yb-4(L)(6)F-6]的连接性由一个环形的Yb-4(Mu-F)(4)外围和两个相对的Yb中心组成，其中一个L配体和一个Yb-2(Mu-F)(2)桥或两个L配体。每个聚氟苯酰胺都表现出来自一个邻位F原子的额外的分子内Yb-F-C配位，从而产生七个或八个Yb中心。以汞(C=-CPH)(2)为汞试剂，通过氧化还原/配体交换反应合成4a，得到了[Yb-4(O)(2)(L)(4)(-CPH)(4)(THF)(2)]中心点四氢呋喃(9a中心点四氢呋喃)，这很可能是初始产物氧化的结果。
Metalation of either N,N-diethyl- or N,N-dimethyl-N'-2,3,5,6-tetrafluorophenylethane-1,2-diamines (HL 1a, 1b respectively) with [M{N(SiMe3)(2)}] (M=Na, K) or [Yb{N(SiMe3)(2)}(2)(thf)(2)] yielded the metalamido compounds [Na(L)) (2a), [K(L)] (3a) and [Yb(L)(2)(thf)(2)] (4a, 4b). The Yb complexes were also synthesised by redox transmetalation/ligand exchange from Yb, Hg(C6F5)(2) and HL in THF or 4a from a reaction of 3a with YbI2 in THE In the presence of N,N,N',N'-tetramethyl-1,2-ethanediamine (TMEDA) the complexes 2a and 3a yielded [Na(L)(2)Na(tmeda)] (5a) and [K-2(L)(2)(tmeda)(2)] (6a), respectively, as crystalline compounds, whilst crystallisation of 4a from DME gave [Yb(L)(2)(dme)] (7a). Their structures have chelating metal-amide and NR2 donors and additional intramolecular M-F-C connectivity with relatively short bond lengths (Na-F 2.65-3.00 angstrom; K-F 2.70-3.00 angstrom; Yb-F 2.56 angstrom). The Yb complexes undergo C-F activation in solution forming [Yb-4(L)(6)F-6] (8a, 8b). The connectivity of [Yb-4(L)(6)F-6], as shown by the X-ray structures, comprised a circular Yb-4(mu-F)(4) periphery with two opposing Yb centres having either one L ligand and a Yb-2(mu-F)(2) bridge or two L ligands. Each polyfluorophenylamide exhibits additional intramolecular Yb-F-C coordination from one of the ortho-F atoms resulting in seven or eight coordinate Yb centres. An attempt to synthesise 4a by redox transmetalation/ligand exchange using Hg(C=-CPh)(2) as the mercury reagent gave [Yb-4(O)(2)(L)(4)(-cPh)(4)(thf)(2)]center dot THF (9a center dot THF), most likely as a result of oxidation of the initially formed product.