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首页> 外文期刊>Chemistry: A European journal >Secondary Interactions in Phosphane-Functionalized Group 4 Cycloheptatrienyl-Cyclopentadienyl Sandwich Complexes
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Secondary Interactions in Phosphane-Functionalized Group 4 Cycloheptatrienyl-Cyclopentadienyl Sandwich Complexes

机译：磷酸功能化的第4组环庚三烯基-环戊二烯基三明治复合物的次级相互作用

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摘要

Phosphane-functionalized cycloheptatrienyl-cyclopentadienyl Group 4 metal complexes of the type [(eta(7)-C7H7)M(eta(5)-C5H4PR2)] (M = Ti (9); M = Zr (10); M = Hf (11); R = Ph (a), R = iPr (b)) have been prepared by the reduction of [eta(5)-C5H4PR2)TiCl3] or [(eta(5)-C5H4PR2)(2)MCl2] (M = Zr, Hf) with magnesium in the presence of cycloheptatriene (C7H8). In the solid state, the Ti complex 9a and the complex 11b are monomeric, whereas 10a, 10b, and 11a form dimers, in which the sandwich units are linked by long Zr-P or Hf-P bonds. Density-functional theory (DFT) calculations indicate that the metal-phosphane interaction is weak, and accordingly, both the Ti complex 9b and the Zr complex 10b act as monodentate phosphane ligands upon reaction with [{(cod)RhCl}(2)] (cod =eta(4)-1,5-cyclooctadiene). The X-ray crystal structures of [(cod)Rh(9b)Cl] (12) and [(cod)Rh(10b)Cl] (13) reveal that only the latter exhibits a secondary intramolecular Cl-metal interaction. The complex [(10b)(2)Pd] (14) was obtained by reaction of [(eta(5)-C5H5)Pd(eta(3)-C3H5)] with two equivalents of 10b. The solid-state structure of 14 reveals a T-shaped Pd-0 center with a long Pd-Zr bond of 2.9709(3) angstrom, which can be interpreted as a weak noncovalent Pd-0 -> Zr+IV bond, as indicated by the calculated relaxed force constant of 5.68 N m(-1).
机译：[[eta（7）-C7H7）M（eta（5）-C5H4PR2）]类型的膦官能化环庚三烯基-环戊二烯基第4组金属配合物（M = Ti（9）; M = Zr（10）; M = Hf （11）; R = Ph（a），R = iPr（b））是通过还原[eta（5）-C5H4PR2）TiCl3]或[（eta（5）-C5H4PR2）（2）MCl2]制备的（M = Zr，Hf）和镁在环庚三烯（C7H8）的存在下。在固态下，Ti络合物9a和络合物11b是单体，而10a，10b和11a形成二聚体，其中夹心单元通过长的Zr-P或Hf-P键连接。密度泛函理论（DFT）计算表明，金属与膦的相互作用较弱，因此，与[{（cod）RhCl}（2）]反应时，Ti络合物9b和Zr络合物10b均充当单齿膦配体。 （鳕鱼＝ eta（4）-1，5-环辛二烯）。 [（cod）Rh（9b）Cl]（12）和[（cod）Rh（10b）Cl]（13）的X射线晶体结构表明，只有后者显示出次级分子内Cl-金属相互作用。配合物[（10b）（2）Pd]（14）是通过[（eta（5）-C5H5）Pd（eta（3）-C3H5）]与两个当量的10b反应获得的。 14的固态结构显示T型Pd-0中心具有2.9709（3）埃的长Pd-Zr键，这可以解释为弱的非共价Pd-0-> Zr + IV键通过计算得出的5.68 N m（-1）的松弛力常数。

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