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.

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.

Dedicated to Professor Nils Wiberg on the occasion of his 70th birthdayThe oxidative metal-mediated C-C coupling reaction of (2-pyridylmethyl)(trialkylsilyl)amines succeeds smoothly with dialkylzinc [Eq. (1)] or tin(ii) bis[bis(trimethylsilyl)amide].[1]The influence of the standard potential as well as the role of the steric demand of the nitrogen-bonded trialkylsilyl and zinc-bonded alkyl groups have been investigated.[2] The Nbonded trialkylsilyl substituent is obligatory to prevent side reactions. The reaction of dialkylzinc with 2-py-CH 2 NH 2 (py = pyridyl) yields several products which can be explained by a combination of oxidative C-C coupling and transamination reactions. After protolysis of this reaction mixture a small amount of cis-1,2-di(2-pyridyl)aminoethene (1; Scheme 1) can be isolated in a reproducible procedure.[3] However, we were not able to detect the zincated 1,2-di(2-pyridyl)aminoethene during the reaction. Amine 1 crystallized as the eneamine tautomer, an equilibrium with the imine tautomer was not detectable with spectroscopic methods.Even 30 years ago, doubly zincated primary amines of the type [RN(ZnR') 2 ] were of interest as catalysts for polymerization reactions, [4] however, these compounds were poorly characterized and more recent attempts to prepare bis(alkylzinc)alkyl-and -arylimides by zincation of primary alkylamines failed. [5,6]

Dedicated to Professor Nils Wiberg on the occasion of his 70th birthdayThe oxidative metal-mediated C-C coupling reaction of (2-pyridylmethyl)(trialkylsilyl)amines succeeds smoothly with dialkylzinc [Eq. (1)] or tin(ii) bis[bis(trimethylsilyl)amide].[1]The influence of the standard potential as well as the role of the steric demand of the nitrogen-bonded trialkylsilyl and zinc-bonded alkyl groups have been investigated.[2] The Nbonded trialkylsilyl substituent is obligatory to prevent side reactions. The reaction of dialkylzinc with 2-py-CH 2 NH 2 (py = pyridyl) yields several products which can be explained by a combination of oxidative C-C coupling and transamination reactions. After protolysis of this reaction mixture a small amount of cis-1,2-di(2-pyridyl)aminoethene (1; Scheme 1) can be isolated in a reproducible procedure.[3] However, we were not able to detect the zincated 1,2-di(2-pyridyl)aminoethene during the reaction. Amine 1 crystallized as the eneamine tautomer, an equilibrium with the imine tautomer was not detectable with spectroscopic methods.Even 30 years ago, doubly zincated primary amines of the type [RN(ZnR') 2 ] were of interest as catalysts for polymerization reactions, [4] however, these compounds were poorly characterized and more recent attempts to prepare bis(alkylzinc)alkyl-and -arylimides by zincation of primary alkylamines failed. [5,6]