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)-2phenylethane (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 893 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.
A two-step synthesis allows the preparation of [α-(2-pyridyl)-benzyl]amine (1) in good yield. Phosphanylation in the presence of triethylamine gives (diphenylphosphanyl)[α-(2-pyridyl)benzyl]amine (2), which crystallizes as a racemate in the centrosymmetric triclinic space group P1. The P-N bond lengths exhibit an average value of 168.3 pm. Lithiation of 2 with n-butyllithium yields dimeric semi(tetrahydrofuran)lithium (diphenylphosphanyl)[α-(2-pyridyl)benzyl]amide (3) with the lithium atoms in different environments. One Li
Metallation of N‐(diphenylphosphanyl)(2‐pyridylmethyl)amine with n‐butyllithium in toluene yields lithium N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide (1), which crystallizes as a tetramer. Transamination of N‐(diphenylphosphanyl)(2‐pyridylmethyl)amine with an equimolar amount of Sn[N(SiMe3)2]2 leads to the formation of monomeric bis(trimethylsilyl)amido tin(II) N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide (2). The addition of another equivalent of N‐(diphenylphosphanyl)(2‐pyridylmethyl)amine gives homoleptic tin(II) bis[N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide] (3). In these complexes the N‐(diphenylphosphanyl)(2‐pyridylmethyl)amido groups act as bidentate bases through the nitrogen bases. At elevated temperatures HN(SiMe3)2 is liberated from bis(trimethylsilyl)amido tin(II) N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide (2) yielding mononuclear tin(II) 1,2‐dipyridyl‐1,2‐bis(diphenylphosphanylamido)ethane (4) through a C–C coupling reaction. The three‐coordinate tin(II) atoms of 2 and 4 adopt trigonal pyramidal coordination spheres.
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