biostudies-literatureArmstrong DREngineering and Physical Sciences Research Council8820-31https://www.ebi.ac.uk/biostudies/studies/S-EPMC3761191biostudies-literatureUnknown17(32)Studied extensively in solution and in the solid state, Li(TMP) (TMP=2,2,6,6-tetramethylpiperidide) is an important utility reagent popular as a strongly basic, weakly nucleophilic tool for C-H metallation. Recently, there has been a surge in interest in mixed metal derivatives containing the bulky TMP anion. Herein, we start to develop hetero (alkali metal) TMP chemistry by reporting the N,N,N',N'-tetramethylethylenediamine (TMEDA)-hemisolvated sodium-lithium cycloheterodimer [(tmeda)Na(μ-tmp)(2) Li], and its TMEDA-free variant [{Na(μ-tmp)Li(μ-tmp)}(∞)], which provides a rare example of a crystallographically authenticated polymeric alkali metal amide. Experimental observations suggest that the former is a kinetic intermediate en route to the latter thermodynamic product. Furthermore, a tChemistry (Weinheim an der Bergstrasse, Germany)Developing a hetero-alkali-metal chemistry of 2,2,6,6-tetramethylpiperidide (TMP): stoichiometric and structural diversity within a series of lithium/sodium, lithium/potassium and sodium/potassium TMP compounds.PMC3761191EP/F063733/1Armstrong DRRobertson SDKennedy ARMulvey REfalseDeveloping a hetero-alkali-metal chemistry of 2,2,6,6-tetramethylpiperidide (TMP): stoichiometric and structural diversity within a series of lithium/sodium, lithium/potassium and sodium/potassium TMP compounds.Studied extensively in solution and in the solid state, Li(TMP) (TMP=2,2,6,6-tetramethylpiperidide) is an important utility reagent popular as a strongly basic, weakly nucleophilic tool for C-H metallation. Recently, there has been a surge in interest in mixed metal derivatives containing the bulky TMP anion. Herein, we start to develop hetero (alkali metal) TMP chemistry by reporting the N,N,N',N'-tetramethylethylenediamine (TMEDA)-hemisolvated sodium-lithium cycloheterodimer [(tmeda)Na(μ-tmp)(2) Li], and its TMEDA-free variant [{Na(μ-tmp)Li(μ-tmp)}(∞)], which provides a rare example of a crystallographically authenticated polymeric alkali metal amide. Experimental observations suggest that the former is a kinetic intermediate en route to the latter thermodynamic product. Furthermore, a t2011-01-01T00:00:00Z2011 Aug2025-04-19T02:34:18.881Z2019-03-27T01:15:27ZS-EPMC37611912176636510.1002/chem.201101167