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首页> 外文期刊>Chemistry: A European journal >Experimental and theoretical investigations of structural isomers of dichalcogenoimidodiphosphinate dimers: Dichalcogenides or spirocyclic contact ion pairs?
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Experimental and theoretical investigations of structural isomers of dichalcogenoimidodiphosphinate dimers: Dichalcogenides or spirocyclic contact ion pairs?

机译：二氯代亚氨基二膦酸酯二聚体的结构异构体的实验和理论研究：双硫属元素化物或螺环接触离子对？

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摘要

A synthetic protocol for the tert-butyl-substituted dichalcogenoimidodiphosphinates [Na(tmeda)-{(EPtBu2)(2)N}] (3a, E = S; 3b, E = Se; 3c, E = Te) has been developed. The one-electron oxidation of the sodium complexes [Na(tmeda){(EPR2)(2)N}] with iodine produces a series of neutral dimers (EPR2NPR2E-)(2) (4b, E = Se, R = iPr; 4c, E = Te, R = iPr; 5a, E = S, R = tBu; 5b, E = Se, R = tBu; 5c, E = Te, R = tBu). Attempts to prepare 4a (E = S, R = iPr) in a similar manner produced a mixture including HN=(SPiPr(2)). Compounds 4b, 4c and 5a-c were characterised by multinuclear NMR spectra and by X-ray crystallography, which revealed two alternative structures for these dimeric molecules. The derivatives 4b, 4c, 5a and 5b exhibit acyclic structures with a central chalcogen-chalcogen linkage that is elongated by approximately 2% (E = S), 6% (E = Se) and 8% (E = Te) compared to typical single-bond values. By contrast, 5c adopts an unique spirocyclic contact ion-pair structure in which a [(TePtBu2)(2)N]- ion is Te,Te' chelated to an incipient [(TePtBu2)(2)N](+) cyclic ion. DFT calculations of the relative energies of the two structural isomers indicate a trend towards increasing stability for the contact ion pair relative to the corresponding dichalcogenide on going from S to Se to Te for both the isopropyl and tert-butyl series. The two-electron oxidation of [Na(tmeda)-{(EPtBu2)(2)N}] (E = S, Se, Te) with iodine produced the salts [(EptBu(2))(2)N]X-+(-) (7 a, E = S, X = 13; 7b, E = Se, X = I; 7c, E = Te, X = I), which were characterised by X-ray crystallography. Compound 7a exists as a monomeric, ion-separated complex with [d(S-S) = 2.084(2) angstrom]; 7b and 7c are dimeric [d(Se-Se) = 2.502(1) angstrom; d(Te-Te) = 2.884(1) angstrom].
机译：已经开发出用于叔丁基取代的二卤代氨基二膦酸酯[Na（tmeda）-{（EPtBu2）（2）N}]（3a，E = S; 3b，E = Se; 3c，E = Te）的合成方案。钠络合物[Na（tmeda）{（EPR2）（2）N}]与碘的单电子氧化产生一系列中性二聚体（EPR2NPR2E-）（2）（4b，E = Se，R = iPr; 4c，E ＝ Te，R ＝ iPr; 5a，E ＝ S，R ＝ tBu; 5b，E ＝ Se，R ＝ tBu; 5c，E ＝ Te，R ＝ tBu）。尝试以类似方式制备4a（E = S，R = iPr）会生成包含HN =（SPiPr（2））的混合物。化合物4b，4c和5a-c通过多核NMR光谱和X射线晶体学表征，揭示了这些二聚体分子的两个替代结构。衍生物4b，4c，5a和5b的无环结构具有中心硫族元素-硫族元素键，与典型值相比，伸长了大约2％（E = S），6％（E = Se）和8％（E = Te）单键值。相比之下，5c采用独特的螺线环接触离子对结构，其中[[（TePtBu2）（2）N]-离子被Te，Te'螯合到起始的[（TePtBu2）（2）N]（+）环离子上。对两种结构异构体的相对能的DFT计算表明，对于异丙基和叔丁基系列，从S到Se到Te时，接触离子对相对于相应的二卤化物的稳定性趋于增加。 [Na（tmeda）-{（EPtBu2）（2）N}]（E = S，Se，Te）与碘的双电子氧化产生了盐[[EptBu（2））（2）N] X- +（-）（7a，E ＝ S，X ＝ 13; 7b，E ＝ Se，X ＝ I; 7c，E ＝ Te，X ＝ I），其通过X射线晶体学表征。化合物7a以离子分离的单体配合物形式存在，[d（S-S）= 2.084（2）埃]; 7b和7c是二聚体[d（Se-Se）＝ 2.502（1）埃; d（Te-Te）= 2.884（1）埃]。

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