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Electronic, Steric, and Ligand Influence on the Solid‐State Structures of Substituted Sodium and Potassium Anilides
Author(s) -
Glock Carsten,
Görls Helmar,
Westerhausen Matthias
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100877
Subject(s) - chemistry , tetramethylethylenediamine , steric effects , denticity , medicinal chemistry , tetrahydrofuran , metalation , salt metathesis reaction , potassium , ligand (biochemistry) , metathesis , stereochemistry , metal , organic chemistry , polymerization , solvent , biochemistry , receptor , polymer
Alkali metal amides are widely used as starting materials in salt metathesis and metalation reactions. N ‐Substituted anilides (phenylamides) of sodium and potassium AN(Ph)R [A = Na, K; R = methyl (Me), isopropyl ( i Pr), phenyl (Ph)] are accessible by transamination with AN(SiMe 3 ) 2 . Neutral coligands, such as ethers and amines, have a strong influence on the solid‐state structures and solubility in common organic solvents. The crystal structures of the following anilides are discussed: [(pmdta)KNPh 2 ] 2 ( 1 ) (pmdta = N , N , N′ , N″,N″ ‐pentamethyldiethylenetriamine), [(pmdta)KN(Ph) i Pr] 2 ( 2 ), [(thf) 2 NaNPh 2 ] 2 ( 3 ) (thf = tetrahydrofuran), [(dme)NaN(Ph) i Pr] 2 ( 4 ) (dme = 1,2‐dimethoxyethane), [(pmdta)NaNPh 2 ] 2 ( 5 ), [(thf) 2 NaN(Ph) i Pr] 2 ( 6 ), [(tmeda)NaN(Ph) i Pr] 2 ( 7 ) (tmeda = N , N , N′ , N′ ‐tetramethylethylenediamine), [(dme) 2 KN(Ph) i Pr] 2 ( 8 ), [(diox) 1.33 NaNPh 2 ] ∞ ( 9 ) (diox = 1,4‐dioxane), [(diox)NaN(Ph) i Pr] ∞ ( 10 ), [KN(Ph)Me] ∞ ( 11 ), [{(thf)KN(Ph) i Pr} 5 ] ∞ ( 12 ), [{(thf)KN(Ph) i Pr} 2 · 2KN(Ph) i Pr] ( 13 ), and [(dme) 0.25 KN(Ph) i Pr] ∞ ( 14 ). All of the sodium anilides contain a central four‐membered Na 2 N 2 ring, whereas the interactions between the cations and the π‐systems of the phenyl groups have an increased importance in the potassium derivatives. Bidentate ether bases such as diox and dme can act as bridging ligands; however, this coordination behavior was not observed for the multidentate amines tmeda and pmdta.