Complexes of manganese, iron and cobalt with sterically demanding indenyl ligands.
Complexes of manganese, iron and cobalt with sterically demanding indenyl ligands.
复制标题
锰、铁和钴与空间要求较高的茚基配体的配合物。
作者：
Miyuki Maekawa;C. Daniliuc;M. Freytag;P. Jones;Marc D. Walter
制备了一系列具有立体要求的1,3-二取代独立基配体1,3-(Me(3)C)(2)C(9)H(5) (Ind(tBu))(1)和1,3-(C(6)H(11))(2)C(9)H(5) (Ind(cHexyl))(2)的锰、铁和钴配合物。这些配合物已经通过各种光谱技术、元素分析和x射线衍射实验得到了充分的表征。此外，还对这些配体的电子和空间性质进行了评价。虽然它们的锥角和电子性质与1,2,4-(Me(3)C)(3)C(5)H(2) （Cp’）相似，但独立基铁半夹层配合物仅在低温下稳定。这已经证明了1-FeI通过适当的捕获实验，如CO或NaCp‘分别产生1-Fe(CO)(2)I和1-FeCp’。总的来说，这些独立基化合物的金属配体键弱于相应的环戊二烯基衍生物。此外，在2-300 K的固体磁化率范围内，双（独立基）锰配合物，1-Mn和2-Mn，是高自旋的。
A series of manganese, iron and cobalt complexes bearing sterically demanding 1,3-disubstituted indenyl ligands, 1,3-(Me(3)C)(2)C(9)H(5) (Ind(tBu)) (1) and 1,3-(C(6)H(11))(2)C(9)H(5) (Ind(cHexyl)) (2), has been prepared. These complexes have been fully characterised by various spectroscopic techniques, elemental analysis, and X-ray diffraction experiments. In addition the electronic and steric properties of these ligands have been evaluated. Although the cone angles and electronic properties are similar to 1,2,4-(Me(3)C)(3)C(5)H(2) (Cp'), indenyl iron half-sandwich complexes are only stable at low temperature. This has been demonstrated for 1-FeI using suitable trapping experiments such as CO or NaCp' addition to yield 1-Fe(CO)(2)I and 1-FeCp', respectively. Overall the metal-ligand bonds in these indenyl compounds are weaker than in the corresponding cyclopentadienyl derivatives. In addition, the bis(indenyl)manganese complexes, 1-Mn and 2-Mn, are high-spin, as established by solid state magnetic susceptibility studies in the temperature range 2-300 K.