Electronic Properties of a Cationic Triphenylphosphine Ligand Decorated with a (η5-C5H5)Fe Group in Late-Transition-Metal Complexes,Organometallics

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Electronic Properties of a Cationic Triphenylphosphine Ligand Decorated with a (η5-C5H5)Fe Group in Late-Transition-Metal Complexes
Organometallics ( IF 2.5 ) Pub Date : 2020-09-07 , DOI: 10.1021/acs.organomet.0c00414
Christian Malchau ₁ , Florian Loose ₁ , Yannick Mees _{1,

2} , Jens Duppe ₁ , Yu Sun ₁ , Gereon Niedner-Schatteburg _{1,

2} , Werner R. Thiel ₁

Affiliation

The synthesis and characterization of a series of novel cationic multimetallic transition-metal complexes based on the cationic phosphine ligand (η⁶-diphenylphosphinobenzene)(η⁵-cyclopentadienyl)iron(II) hexafluorophosphate (1) are reported. Complexes of ligand 1 with the late transition metals ruthenium, osmium, rhodium, and iridium as well as palladium and platinum were isolated in generally good yields, and the solid-state structures of most of them were determined. On the basis of the ¹⁹⁵Pt–³¹P NMR coupling constant measured for trans-(1)₂PtCl₂ and the carbonyl absorption band in the IR spectrum of trans-(1)₂Rh(CO)Cl, the electronic influence of the ligand on the metal center was evaluated. These measurements are supported by density functional theory (DFT) calculations, performed on the corresponding tricarbonylnickel(0) complex in order to determine the Tolman electronic parameter (TEP) of ligand 1.

中文翻译：

阳离子配体三苯基膦的装饰电子性质用（η ⁵ -C ₅ H ^ ₅）的Fe组晚-过渡金属配合物

一系列基于阳离子膦配位体（η新型阳离子多金属的过渡金属配合物的合成和表征⁶ -diphenylphosphinobenzene）（η ⁵ -环戊二烯基）铁（II）六氟磷酸盐（1被报告）。配体1与后期过渡金属钌，，铑和铱以及钯和铂的配合物通常以良好的收率被分离出来，并确定了其中大多数的固态结构。根据对反式-（1）₂ PtCl ₂测得的¹⁹⁵ Pt– ³¹ P NMR偶联常数并通过反式-（1）₂ Rh（CO）Cl的红外光谱中的羰基吸收带，评估了配体对金属中心的电子影响。这些测量得到相应的三羰基镍（0）配合物进行的密度泛函理论（DFT）计算的支持，以确定配体1的Tolman电子参数（TEP）。

更新日期：2020-09-28

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