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Syntheses of N ‐(Diphenylphosphanyl)‐2‐pyridylmethylamine and Its Use as a Ligand in Magnesium and Zinc Complexes
Author(s) -
Olbert Dirk,
Kalisch Alexander,
Herzer Nicole,
Görls Helmar,
Mayer Peter,
Yu Lian,
Reiher Markus,
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.200700024
Subject(s) - chemistry , amide , medicinal chemistry , electrophile , tetrahydrofuran , ligand (biochemistry) , zinc , lithium (medication) , magnesium , denticity , amine gas treating , metal , organic chemistry , solvent , catalysis , medicine , biochemistry , receptor , endocrinology
The metathesis reaction of lithium 2‐pyridylmethylamide with chloroalkanes and phosphanes yields N ‐ and C ‐substitution products depending on the electrophile. Thus, C ‐alkylated 1‐amino‐1‐(2‐pyridyl)‐2,2‐dimethylpropane ( 1 ) and 1‐amino‐1‐(2‐pyridyl)‐2‐phenylethane ( 2 ) and N ‐substituted N ‐benzyl‐(2‐pyridylmethyl)amine ( 3 ) and N ‐(diphenylphosphanyl)‐2‐pyridylmethylamine ( 4 ) are obtained. In [ 1· LiCl] 2 , molecule 1 binds to the lithium atom in a bidentate fashion. C ‐ and N ‐ substituted 2‐pyridylmethylamines are compared with quantum chemical methods. Lithiation of 4 and subsequent reaction with cloro‐diphenylphosphane yields N , N ‐bis(diphenylphosphanyl)‐2‐pyridylmethylamine ( 5 ) with a planar amine nitrogen atom. Metallation of 4 with dibutylmagnesium leads to the formation of colorless (tetrahydrofuran)magnesium bis[ N ‐(diphenylphosphanyl)‐2‐pyridylmethylamide] ( 6 ) with a penta‐coordinate alkaline earth metal atom in a trigonal bipyramidal environment. In contrast to this observation, the reaction of 4 with dimethylzinc yields colorless methylzinc bis[ N ‐(diphenylphosphanyl)‐2‐pyridylmethylamide] ( 7 ). Zincation of 1 gives dimeric methylzinc 1‐(2‐pyridyl)‐2,2‐dimethyl‐1‐propylamide ( 8 ). In these zinc complexes the metal and amide nitrogen atoms are in distorted tetrahedral environments.