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首页> 外文期刊>RSC Advances >Synthesis, coordination behavior and structural features of chiral iron(ii) PNP diferrocene complexes
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Synthesis, coordination behavior and structural features of chiral iron(ii) PNP diferrocene complexes

机译：手性铁（II）PNP Direrocene复合物的合成，协调行为和结构特征

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摘要

Five new chiral PNP ferrocene ligands with either an imine or amine nitrogen coordination site were synthesized. Only the imine type ligands formed Fe( II ) complexes with the general formula [Fe(PNP)X _(2) ] (X = Cl, Br). In the solid state these complexes adopt a tetrahedral geometry with the PNP ligand coordinated in a κ ~(2) P,N-fashion with the one pendant-arm and the other not coordinated, as determined by X-ray crystallography and M?ssbauer spectroscopy. The complexes are paramagnetic with a quintet ground state. In solution there is an equilibrium between [Fe(κ ~(3) P,N,P-PNP)X _(2) ] and [Fe(κ ~(2) P,N-PNP)X _(2) ] complexes. Boronation of the non-coordinated arm shifts the equilibrium towards the four-coordinate complex [Fe(κ ~(2) P,N-PNP ~(BH _(3) ) )Br _(2) ]. DFT calculations are consistent with the experimental results and indicate that the experimentally observed κ ~(2) isomer is thermodynamically the most stable. In a CO atmosphere, [Fe(PNP)(CO) _(2) Br]Br was formed rather than [Fe(PNP)(CO)Br _(2) ].
机译：合成了具有亚胺或胺氮气配位部位的五种新的手性PNP二茂铁配体。只有亚胺型配体形成Fe（II）配合物，其中通式[Fe（PNP）X _（2）]（X = Cl，Br）。在固态中，这些配合物采用四面体几何形状，与κ〜（2）P，N时时配位的PNP配体，与X射线晶体学和M？Ssbauer测定光谱学。复合物是Quintet地面状态的顺磁性。在解决方案中，[Fe（κ〜（3）p，n，p-pnp）x _（2）]和[Fe（κ〜（2）p，n-pnp）x _（2）之间存在平衡。复合物。非协调臂的硼化朝向四坐标综合体的平衡[Fe（κ〜（2）p，n-pnp〜（bh _（3）））br _（2）]。 DFT计算与实验结果一致，并表明实验观察到的κ〜（2）异构体是最稳定的热力学上。在CO气氛中，形成[Fe（PNP）（CO）_（2）BR] BR而不是[Fe（PNP）（CO）BR _（2）]。

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