Rhodium(III) and Ruthenium(II) Complexes with a Pentadentate Tetrapodal Phosphine Ligand,Zeitschrift für anorganische und allgemeine Chemie

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Rhodium(III) and Ruthenium(II) Complexes with a Pentadentate Tetrapodal Phosphine Ligand
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2021-01-15 , DOI: 10.1002/zaac.202000455
Jannik Junge , Tobias A. Engesser , Jan Krahmer , Christian Näther , Felix Tuczek ₁

Affiliation

Rhodium(III) and ruthenium(II) complexes supported by a pentadentate tetrapodal (pentaPod) phosphine ligand are synthesized through abstraction of one chloride ligand from initially obtained κ⁴‐pentaPod coordinated dichloro complexes [MCl₂(κ⁴‐P₂^MePP₂^Ph)]^+/0 (M=Rh(III), Ru(II)) with alkali salts of weakly coordinating anions. While for the rhodium κ⁵‐pentaPod complex the remaining, axial chloride ligand could not be replaced by di‐ or triatomic ligands, in case of ruthenium the complexes [Ru(CN)(κ⁵‐P₂^MePP₂^Ph]Al(pftb)₄ (5) and [Ru(N₃)(κ⁵‐P₂^MePP₂^Ph]Al(pftb)₄ (6) could be generated through ligand exchange. By comparison of NMR parameters and employing DFT calculations, additional insights into the electronic influence of different ligands (i. e., Cl⁻, CN⁻, N₃⁻) could be gained.

中文翻译：

铑（III）和钌（II）与五齿四足膦配体的配合物

铑（III）和钌由五齿tetrapodal（支持的（II）配合物pentaPod）膦配位体是通过一种氯化物配体的抽象从最初得到的合成κ ⁴ - pentaPod协调二氯络合物[的MC1 ₂（κ ⁴ -P ₂^我PP ₂^Ph）] ^{+ / 0}（M = Rh（III），Ru（II））与弱配位阴离子的碱金属盐。而对于铑κ ⁵ - pentaPod复杂剩余的轴向配体氯化物不能由二-或三原子配位体来代替，在钌配合物的[Ru（CN）（的情况下，κ⁵ -P ₂^我PP ₂^博士]的Al（pftb）₄（5）和[茹（N ₃）（κ ⁵ -P ₂^我PP ₂^博士]的Al（pftb）₄（6）可被通过配体交换生成。通过NMR参数和采用DFT计算，额外的见解的比较成不同的配位体的电子影响（即，氯^-，CN ^-，N ₃^-）可被获得。

更新日期：2021-01-15

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