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Synthesis of Ni(II) Complexes Supported by Tetradentate Mixed-Donor Bis(amido)/Phosphine/Phosphido Ligands by Phosphine Substituent Elimination
Organometallics ( IF 2.5 ) Pub Date : 2020-05-26 , DOI: 10.1021/acs.organomet.0c00286
Kyounghoon Lee 1 , Curtis E. Moore 1 , Christine M. Thomas 1
Affiliation  

A convenient nickel-templated phenyl elimination route is described for the synthesis of phosphide-containing multidentate ligands from triarylphosphine precursors. Treating Ni(COD)2 with the neutral bis(amine)/bis(phosphine) ligand precursor H24Ph[PNNP] affords bis(amido)/bis(phosphine) complex 1. Treatment of 1 with 1 equiv of KH leads to elimination of a phenyl group from one of the phosphine fragments, generating bis(amido)/phosphine/phosphido complex 3Ph[PNNP]Ni (2). Alternatively, excess KH or nBuLi affords the bis(amido)/bis(phosphide) complex 2Ph[PNNP]Ni2– (3 or 4, respectively) by elimination of two phenyl substituents. These reactions are high-yielding and provide a unique and straightforward route to chelating phosphido ligands that would otherwise be challenging to synthesize.

中文翻译:

磷取代基消除合成四齿混合供体双(酰胺基)/膦/磷配体负载的Ni(II)配合物

描述了一种方便的镍模板化的苯基消除途径,用于从三芳基膦前体合成含磷的多齿配体。用中性双(胺)/双(膦)配体前体H 2 4Ph [PNNP]处理Ni(COD)2可获得双(酰胺基)/双(膦)配合物1。用1当量的KH处理1会导致从一个膦片段中消除一个苯基,从而生成双(酰胺基)/膦/磷复合物3Ph [PNNP] Ni 2)。或者,过量的KH或n BuLi可提供双(酰胺基)/双(磷化物)络合物2Ph [PNNP] Ni通过消除两个苯基取代基可得到2-(分别为34)。这些反应是高产率的,并提供了螯合磷配体的独特而直接的途径,否则将难以合成。
更新日期:2020-05-26
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