Synthetic and reactivity studies of hetero-tri-anionic sodium zincates.
Synthetic and reactivity studies of hetero-tri-anionic sodium zincates.
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杂三阴离子锌酸钠的合成和反应性研究。
DOI：
10.1039/c5dt04329h
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Francos J
中科院分区：
文献类型：
--
作者：
Francos J
报道了几种锌酸钠配合物的合成和表征。以等摩尔量的t2zn、nBuNa和PMDETA （N，N,N ',N ',N ' -五甲基二乙烯三胺）为原料，合成了全烷基单体锌酸钠（PMEDTA）·Na(μ-CH2SiMe3)ZntBu22。采用类似的方法制备并分离了罕见的二聚锌酸盐[（PMEDTA）·Na(μ-nBu)ZntBu2]23。当nBuNa、tBu2Zn和TMP(H)（2,2,6,6-四甲基哌啶）的等摩尔混合物在己烷中结合时，得到杂三抗药TMP(H)溶剂化锌酸盐（TMPH）Na(μ-TMP)(μ-nBu) zntbu4。配合物4也可以用合理的方法制备[即，利用两个摩尔当量的TMP(H)]。当TMEDA与nBuNa、tBu2Zn和TMP(H)的等摩尔混合物反应时，得到了单体锌酸钠（TMEDA）Na(μ-TMP)(μ-nBu)ZntBu 5，该配合物在结构上与合成有用关系（TMEDA）·Na(μ-TMP)(μ-tBu)Zn(tBu) 1相似。通过改变合成5所用的钠试剂，可以制备（TMEDA）Na(μ-TMP)(μ-Me3SiCH2)ZntBu 6。通过与顺式dmp (H)（顺式2,6-二甲基哌啶）反应，锌酸盐可以在热力学上起酰胺碱的作用，得到转氨化产物（TMEDA）Na(μ-顺式dmp)(μ-nBu)ZntBu 7，但不能生长晶体。然而，当HMDS(H)（1,1,1,3,3,3-六亚甲基二氮杂烷）或PEA(H)[(+)-双[(R)-1-苯乙基]胺]与5反应时，分别分离出晶体（TMEDA）Na(μ-HMDS)(μ-nBu)ZntBu 8或（TMEDA）Na(μ-PEA)(μ-nBu)ZntBu 9。PNA(H) （n-苯萘-1-胺）的反应过程不同，形成二聚体酰胺钠络合物[(TMEDA)Na(PNA)]210。当与苯反应时，5的无TMEDA变体似乎在热力学上作为nBu碱起作用，生成（TMEDA）Na(μ-TMP)(tBu)Zn(μ-C6H4)Zn(tBu)(μ-TMP)Na(TMEDA) 11。最后与TEMPO（2,2,6,6-四甲基胡椒酰氧基）反应后，5发生单电子转移反应生成（TMEDA）Na(μ-TMP)(μ-TEMPO)ZnnBu 12。
The synthesis and characterisation of several sodium zincate complexes are reported. The all-alkyl monomeric sodium zincate, (PMEDTA)·Na(μ-CH2SiMe3)ZntBu22, is prepared by combining equimolar quantities of tBu2Zn, nBuNa and PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine)]. A similar approach was used to prepare and isolate the unusual dimeric zincate [(PMEDTA)·Na(μ-nBu)ZntBu2]23. When an equimolar mixture of nBuNa, tBu2Zn and TMP(H) (2,2,6,6-tetramethylpiperidine) is combined in hexane, the hetero-tri-leptic TMP(H)-solvated zincate (TMPH)Na(μ-TMP)(μ-nBu)ZntBu 4 results. Complex 4 can also be prepared using a rational approach [i.e., utilising two molar equivalents of TMP(H)]. When TMEDA is reacted with an equimolar mixture of nBuNa, tBu2Zn and TMP(H), the monomeric sodium zincate (TMEDA)Na(μ-TMP)(μ-nBu)ZntBu 5 was obtained – this complex is structurally similar to the synthetically useful relation (TMEDA)·Na(μ-TMP)(μ-tBu)Zn(tBu) 1. By changing the sodium reagent used in the synthesis of 5, it was possible to prepare (TMEDA)Na(μ-TMP)(μ-Me3SiCH2)ZntBu 6. By reacting 5 with cis-DMP(H) (cis-2,6-dimethylpiperidine), the zincate could thermodynamically function as an amide base, to give the transamination product (TMEDA)Na(μ-cis-DMP)(μ-nBu)ZntBu 7, although no crystals could be grown. However, when HMDS(H) (1,1,1,3,3,3-hexamethyldisilazane) or PEA(H) [(+)-bis[(R)-1-phenylethyl]amine] is reacted with 5, crystalline (TMEDA)Na(μ-HMDS)(μ-nBu)ZntBu 8 or (TMEDA)Na(μ-PEA)(μ-nBu)ZntBu 9 is isolated respectively. With PNA(H) (N-phenylnaphthalen-1-amine) the reaction took a different course and resulted in the formation of the dimeric sodium amide complex [(TMEDA)Na(PNA)]210. When reacted with benzene, it appears that a TMEDA-free variant of 5 functions thermodynamically as an nBu base to yield the previously reported (TMEDA)Na(μ-TMP)(tBu)Zn(μ-C6H4)Zn(tBu)(μ-TMP)Na(TMEDA) 11. Finally when reacted with TEMPO (2,2,6,6-tetramethylpiperidinyloxy), 5 undergoes a single electron transfer reaction to form (TMEDA)Na(μ-TMP)(μ-TEMPO)ZnnBu 12.
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影响因子：
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