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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Insight into the stereoelectronic parameters of N-triphos ligands via coordination to tungsten(0)
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Insight into the stereoelectronic parameters of N-triphos ligands via coordination to tungsten(0)

机译：通过与钨的配位了解N-triphos配体的立体电子参数（0）

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摘要

A series of new N-triphos tungsten complexes have been synthesised and structurally characterised. The coordination behaviour of a range of N-triphos (N(CH2PR2)(3), NP3R) ligands, and a mixed-arm diphosphine-pyridyl (PPNCyh) ligand were explored. The steric and electronic parameters of five N-triphos ligands: NP3Ph, NP3iPr, NP3Cyp, NP3Cyh and NP3PhF2, and the carbon-centred triphos ligand, CH3C-(CH2PPh2)(3) (MeCP3Ph), were established. Steric parameters were evaluated by analysing the cone angles calculated from X-ray crystal structures, whilst the electron-donating ability of the ligands was determined from P-31-Se-77 NMR coupling constants of selenium derivatives and the IR carbonyl stretching frequencies across a series of tungsten-carbonyl complexes. In general, electron-rich phosphines formed bidentate complexes while less electron-rich ligands coordinated in a tridentate mode, regardless of steric bulk. An indirect interaction between the apical nitrogen of the ligand and metal centre is implicated for tridentate complexes and is supported through DFT calculations and analysis of N-protonated complexes. Complexes 1, 3, 4, 6-8 and 10 were characterised by single-crystal X-ray crystallography.
机译：已经合成了一系列新的N-三磷钨配合物并进行了结构表征。探索了一系列的N-triphos（N（CH2PR2）（3），NP3R）配体和混合臂二膦-吡啶基（PPNCyh）配体的配位行为。建立了五个N-triphos配体的空间和电子参数：NP3Ph，NP3iPr，NP3Cyp，NP3Cyh和NP3PhF2，以及以碳为中心的三重配体CH3C-（CH2PPh2）（3）（MeCP3Ph）。通过分析由X射线晶体结构计算出的锥角来评估立体参数，而配体的给电子能力由硒衍生物的P-31-Se-77 NMR偶联常数和在整个表面上的IR羰基拉伸频率确定。系列的羰基钨配合物。通常，富电子的膦形成二齿配合物，而富电子的配体以三齿模式配位，而与空间体积无关。三齿配合物暗示配体顶部氮原子与金属中心之间的间接相互作用，并通过DFT计算和N质子化配合物的分析得到支持。配合物1、3、4、6-8和10通过单晶X射线晶体学表征。

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