Reaction of β-diketiminate tin(ii) dimethylamide LSnNMe_2 [L = HC(CMeNAr)_2; Ar = 2,6-iPr_2C_6H_3] with ketones and alkynes

摘要

The reactions of stable β-diketiminate tin(ii) dimethylamide LSnNMe_2 [L = HC(CMeNAr)_2; Ar = 2,6-iPr_2C _6H_3] (1) with ketones and activated terminal alkynes are described. 1 reacts with 2-benzoylpyridine and 2,2,2-trifluoroacetophenone to give the tin(ii)-alkoxides LSnOCPh(2-Py)NMe_2 (2) and LSnOCPh(CF _3)NMe_2 (3), respectively, by nucleophilic addition of the dimethylamido group to the carbonyl moiety. Furthermore, the reaction of 1 with terminal alkynes (HCCCO_2R, R = Me, Et) forms tin(ii)-alkynyl LSnCCCO_2R (R = Me, (4); R = Et, (5)) compounds under elimination of Me_2NH rather than undergoing a nucleophilic addition reaction at the carbon-carbon triple bond. Compounds 2-5 were characterized by microanalysis and multinuclear NMR spectroscopy. Moreover, 2 and 5 could be crystallized and their constitutions were confirmed by X-ray structural analysis. 2 and 5 are monomers in the solid state and the metal atom shows a distorted trigonal-pyramidal coordination sphere.