A practical procedure for the synthesis of N,N,N′,N′-tetramethylethylene diamine nickel dimethyl, [(tmeda)Ni(CH₃)₂] (5), based on commercially available methyllithium and [(tmeda)Ni(acac)₂] (1) (acac = acetylacetonate), [(tmeda)Ni(OAc)₂] (2) (OAc = acetate), [(tmeda)NiSO₄] (3), or [(tmeda)NiF₂] (4) has been developed. With 2 as the starting material, reproducible isolation of >14 g (ca. 68 mmol, 85%) of 5 in one-batch reactions is feasible. This synthetic route also enables the formation and isolation of ¹³C-labeled [(tmeda)Ni(¹³CH₃)₂] (5-¹³CH₃) starting from ¹³CH₃I by intermediate isolation of [(tmeda)_2–3(Li¹³CH₃)₄]_x (10). The amount of iodide impurities in 10 to push back iodide-catalyzed decomposition of 5-¹³CH₃ to ethane and nickel black by a Kumada-type coupling is essential for successful isolation of 5-¹³CH₃. [(tmeda)Ni(OAc)₂] (2) is a superior nickel precursor to 5 in comparison to [(tmeda)Ni(acac)₂] (1), as (a) removal of lithium acetate (9) from the crude reaction mixture is much easier than removal of lithium acetylacetonate and (b) κ²-N,O-salicylaldiminato nickel methyl complexes (12) or a κ²-P,O-phosphinesulfonato nickel methyl complex (14) can be easily prepared in a one-pot procedure starting from 2, methyllithium, and salicylaldimines (11) or phosphoniumsulfonate (13), respectively. The X-ray diffraction analyses of 2, 5, and 12b-PPh₃ are reported.

中文翻译：

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[（tmeda）Ni（CH ₃）₂ ]，同位素标记的[（tmeda）Ni（¹³ CH ₃）₂ ]和中性螯合镍甲基络合物的实用合成

基于市售的甲基锂和[（tmeda）Ni（acac），合成N，N，N ' ，N'-四甲基乙二胺镍二甲基，[（tmeda）Ni（CH ₃）₂ ]（5）的实用程序）₂ ]（1）（acac =乙酰丙酮酸），[（tmeda）Ni（OAc）₂ ]（2）（OAc =乙酸盐），[（tmeda）NiSO ₄ ]（3）或[（tmeda）NiF ₂ ] （4）已开发。以2为起始原料，可重现> 14 g（约68 mmol，85％）的5单批反应是可行的。这种合成途径还可以通过中间分离[[tmeda）_2–3从¹³ CH ₃ I开始形成和分离¹³ C标记的[（tmeda）Ni（¹³ CH ₃）₂ ]（5- ¹³ CH ₃）。（Li ¹³ CH ₃）₄ ] _x（10）。的碘化物杂质的量10推回碘化物催化分解5- ¹³ CH ₃乙烷和镍黑色由熊田型偶联是成功的隔离必不可少5- ¹³ CH ₃。与[（tmeda）Ni（acac）₂ ]（1）相比，[（tmeda）Ni（OAc）₂ ]（2）是优于5的镍前体，因为（a）从硅中去除了乙酸锂（9）。粗反应混合物比除去的乙酰丙酮化锂和（b）κ容易得多² - N，O -salicylaldiminato镍甲基络合物（12）或κ ² -P，O- -phosphinesulfonato镍甲基络合物（14）可以很容易地通过一锅法分别从2，甲基锂和水杨醛亚胺（11）或phospho磺酸盐（13）开始制备。的X射线衍射分析2，5，和图12B-PPH ₃中报告。