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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Bisphosphine monoxides with o-phenylene backbones in Pt, Pd and Fe complexes
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Bisphosphine monoxides with o-phenylene backbones in Pt, Pd and Fe complexes

机译：Pt，Pd和Fe配合物中具有邻亚苯基骨架的一氧化二膦

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A new route to aromatic bisphosphine monoxides has been explored through ortholithiation of triphenylphosphine oxide and subsequent reaction of the lithiated intermediate with a range of alkyl and aryl phosphine chlorides. Routes to the known bisphosphine monoxide (BMPO) (o-C6H4){P(O)Ph-2}PPh2 (2aO) and a range of new BPMOs of the type Ph2P(O)(o-C6H4)PR2 where R-2 = Pr-i(2), Cy-2, Et-2 are described. Reaction of 2aO with MCl2(cod) (M = Pd, PC: cod = cyclooctadiene) gives products of the form [MCl(kappa(1)-P-2aO)( kappa(2)-P,O-2aO)](+) Cl- and MCl2(kappa(2)-P,O-2aO): the former exhibits fluxional behaviour which has been analysed by Pt-195 NMR and (31)p variable-temperature NMR spectroscopy. The bidentate complex is not fluxional for either the Pd or the PC example; the PC Complex PtCl2(kappa(2)-P,O-2aO) has been characterised by X-ray crystallography. By comparison of the product distribution seen by P-31 NMR spectroscopy and ESI-MS it was established that the different coordination modes of 2aO result in quite different behaviour of the complexes when Studied by ESI-MS: when the O is formally coordinated to the metal its ionisation efficiency is very low. Synthesis of Fe(CO)(4)(2aO) confirmed the ability of the 2aO ligand to render a neutral complex with no alternative pathways for ionisation to be readily detected by ESI-MS.
机译：通过三苯膦氧化物的正石化反应以及随后的锂化中间体与一系列烷基和芳基膦氯化物的反应，已经探索出一种新的芳族双膦一氧化碳途径。路由到已知的一氧化二膦（BMPO）（o-C6H4）{P（O）Ph-2} PPh2（2aO）和一系列新的Ph2P（O）（o-C6H4）PR2类型的BPMO，其中R-2 ＝ Pr-1（2），Cy-2，Et-2。 2aO与MCl2（cod）的反应（M = Pd，PC：cod =环辛二烯）得到的形式为[MCl（kappa（1）-P-2aO）（kappa（2）-P，O-2aO）] [ +）Cl-和MCl2（kappa（2）-P，O-2aO）：前者表现出通量行为，已通过Pt-195 NMR和（31）p可变温度NMR光谱分析。对于Pd或PC实例，双齿络合物不是流动的。 PC络合物PtCl2（kappa（2）-P，O-2aO）已通过X射线晶体学表征。通过比较P-31 NMR光谱仪和ESI-MS的产物分布，可以确定，当通过ESI-MS研究时，2aO的不同配位模式会导致络合物的行为完全不同：金属的电离效率非常低。 Fe（CO）（4）（2aO）的合成证实了2aO配体具有中性复合物的能力，而ESI-MS则很容易检测到没有其他电离途径。

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