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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, spectroscopic characterisation and transmetalation of lithium and potassium diaminophosphanide-boranes
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Synthesis, spectroscopic characterisation and transmetalation of lithium and potassium diaminophosphanide-boranes

机译：锂和钾二氨基磷酸 - 硼酸锂的合成，光谱表征和透射率

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摘要

A secondary diaminophosphane-borane (Et2N)(2)PH(BH3) was prepared from a chlorophosphane precursor and LiBH4 and metalated by reaction with anion bases (n-BuLi, KN(SiMe3)(2)) to yield the corresponding metal diaminophosphanide-boranes [(Et2N)(2)PH(BH3)] M (M = Li, K). Multinuclear NMR studies permitted the first spectroscopic characterisation of the metalation products and revealed the presence of monomeric (for M = Li) contact ion pairs in solution. NMR spectroscopic evidence that the ions in each pair interact via Li ... P-rather than Li ... H3B-interactions as had been inferred for a Ph-substituted analogue was confirmed by DFT studies, which revealed also that the borane coordination plays a decisive role in boosting the PH-acidity of the original secondary diaminophosphane precursor. Transmetalation of the potassium and lithium diaminophosphanide-boranes with Cu(I) and Zn(II) chlorides afforded the first functional transition metal complexes of a P-heteroatom-functionalised phosphanide-borane ligand. Both products were fully characterised. Thermolysis of the Cu-complex induced a reaction which involved transfer of an NHC ligand from the metal to the phosphorus atom and yielded a phosphaalkene NHC=PH (NHC = N-heterocyclic carbene) as the major phosphorus-containing product.
机译：由氯膦前体和物质磷酸盐制备仲二氨基磷酸硼烷（Et 2N）（2）pH（BH3），并通过与阴离子碱（N- Buli，KN（SIME3））反应金属化，得到相应的金属二氨基磷酸 - 硼烷[（Et 2N）（2）pH（BH3）] M（m = Li，K）。多核NMR研究允许金属化产品的第一光谱表征，并揭示了溶液中的单体（用于M = Li）的触点离子对的存在。 NMR光谱证据表明，每对的离子通过Li ... p相互作用，而不是Li ... H3B-相互作用，通过DFT研究证实了pH-取代的类似物，这也揭示了硼烷协调扮演促进原仲二氨基磷前体的pH-酸度的决定性作用。用Cu（I）和Zn（II）氯化物的钾和锂二氨基磷酸硼烷的透射率为P-杂原子官能化磷酸硼烷配体提供第一功能过渡金属配合物。两种产品都完全表征。 Cu-复合物的热解诱导反应，其涉及从金属转移到磷原子中的NHC配体，并得到磷烯NHC = pH（NHC = N-杂环切菜）作为主要的含磷产品。

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