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Monomeric Homoleptic (2‐Pyridylmethyl)(tert‐butyldimethylsilyl)amido Complexes of the Divalent Metals Mg, Mn, Fe, Co, and Zn
Author(s) -
Koch Christian,
Malassa Astrid,
Agthe Christine,
Görls Helmar,
Biedermann Ralf,
Krautscheid Harald,
Westerhausen Matthias
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200600307
Subject(s) - homoleptic , chemistry , amide , medicinal chemistry , toluene , lithium amide , amine gas treating , zinc , tin , trimethylsilyl , denticity , metal , inorganic chemistry , stereochemistry , organic chemistry , catalysis , enantioselective synthesis
The transamination reaction of M[N(SiMe 3 ) 2 ] 2 with (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amine yields the corresponding homoleptic metal bis[(2‐pyridylmethyl)(tert‐butyldimethylsilyl)amides] of Mg ( 1 ), Mn ( 2 ), Fe ( 3 ), Co ( 4 ) and Zn ( 5 ). All these compounds crystallize from hexane isotypic in the space group C 2/c. From toluene the zinc derivative precipitates as toluene solvate 5 ·toluene. The molecular structures of these compounds are very similar with large NMN angles to the amide nitrogen atoms with NMN values of 148° ( 1 ) and 150° ( 5 ) for the diamagnetic compounds and 156° for the paramagnetic derivatives 2 and 3 . The Co derivative 4 displays a rather small NCoN angle of 142°. Different synthetic routes have been explored for compound 3 which is also available via the metallation reaction of bis(2,4,6‐trimethylphenyl)iron with (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amine and via the metathesis reaction of lithium (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amide with [(thf) 2 FeCl 2 ]. In course of the metathesis reaction, an equimolar amount of lithium (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amide and [(thf) 2 FeCl 2 ] yields heteroleptic (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amido iron(II) chloride ( 6 ) which crystallizes as a centrosymmetric dimeric molecule. The oxidative C‐C coupling reaction of 5 with Sn[N(SiMe 3 ) 2 ] 2 leads to the formation of tin(II) 1,2‐bis(2‐pyridyl)‐1,2‐bis(tert‐butyldimethylsilylamido)ethane, tin metal and Zn[N(SiMe 3 ) 2 ] 2 .