A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand: Synthesis and reactivity

Liang L.-C.; Li C.-W.; Lee P.-Y.; Chang C.-H.; Man Lee H.

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A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand: Synthesis and reactivity

机译：末端镍（II）苯胺配合物，具有不对称取代的酰胺钳配体：合成和反应性

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This work describes preparation and reaction chemistry of a terminal nickel(ii) anilide complex supported by an unsymmetrically substituted diarylamido diphosphine ligand, [N(o-C_6H_4PPh _2)(o-C_6H_4P~iPr_2)] ~- ([Ph-PNP-~iPr]_-). Treatment of NiCl _2(DME) with H[Ph-PNP-~iPr] in THF at room temperature produced [Ph-PNP-~iPr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP-~iPr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP-~iPr]NiNHPh as a greenish blue solid. The anilide complex deprotonates protic (e.g., PhOH and PhSH) and aprotic (e.g., trimethylsilylacetylene, phenylacetylene, and acetonitrile) acids in benzene at room temperature to give quantitatively [Ph-PNP-~iPr]NiX (X = OPh, SPh, CCSiMe_3, CCPh, CH_2CN). In addition, [Ph-PNP- ~iPr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP-~iPr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP-~iPr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP-~iPr]Ni[C(O) NHPh]. The relative bond strengths of Ni-E in [Ph-PNP-~iPr]NiEPh (E = NH, O, S, CC) are assessed and discussed.

机译：这项工作描述了由不对称取代的二芳基氨基二膦配体[N（o-C_6H_4PPh _2）（o-C_6H_4P〜iPr_2）] ~~（[Ph-PNP-〜 iPr] _-）。在室温下用H [Ph-PNP-〜iPr]在THF中处理NiCl _2（DME），生成[Ph-PNP-〜iPr] NiCl为绿色晶体，产率为82％。 [Ph-PNP-iPr] NiCl与LiNHPh（THF）在-35°C的THF中进行盐易位，生成干净的[Ph-PNP-iPr] NiNHPh，为浅蓝色固体。苯胺复合物在室温下使质子（例如PhOH和PhSH）和非质子（例如三甲基甲硅烷基乙炔，苯乙炔和乙腈）酸去质子化，定量得到[Ph-PNP-〜iPr] NiX（X = OPh，SPh，CCSiMe_3 ，CCPh，CH_2CN）。此外，[Ph-PNP-〜iPr] NiNHPh也可作为亲核试剂与乙酰氯反应，定量生成[Ph-PNP-〜iPr] NiCl和N-苯基乙酰胺。 [Ph-PNP-〜iPr] NiNHPh用一氧化碳羰基化可干净地提供氨基甲酰基衍生物[Ph-PNP-〜iPr] Ni [C（O）NHPh]。评估并讨论了[Ph-PNP-〜iPr] NiEPh中Ni-E的相对键强度（E = NH，O，S，CC）。

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《Dalton transactions: An international journal of inorganic chemistry》 |2011年第35期|共8页
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Liang L.-C.; Li C.-W.; Lee P.-Y.; Chang C.-H.; Man Lee H.;
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机译：末端镍（II）苯胺配合物，具有不对称取代的酰胺钳配体：合成和反应性
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A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand: Synthesis and reactivity

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