Beiträdge zur chemie organometallischer metallacyclischer nebengruppenmetallverbindungen: VIII. Synthese und Eigenschaften von Li 2[formula omitted]-(CH 2(CH 2) 2C H 2) 2 (D) x - Molekülstruktur von [Li(THF) 2] 2[formula omitted]H 2) 2

Abstract

[(Et 2O)Li 2 Pd-(CH 2(CH 2) 2C H 2) 2] ( 1) was prepared by treatment of (1,5-COD)PdCl 2 with Li(C 4H 8)Li in diethyl ether. By substituting other n-donor for the diethyl ether in 1, derivatives of the composition [(D) x Li 2 Pd(CH 2(CH 2) 2C H 2) 2] (D= N, N, N′, N′-tetramethylethylenediamine (TMEDA), x = 2 ( 2); N, N, N′, N′, N″-pentamethyldiethylenetriamine (PMDETA), x = 2 ( 3); tetrahydrofuran (THF), x = 4 ( 4)) are obtained. The complexes 1-4 have been characterized by elemental and DTA analysis, and complexes 2 and 3 by 1H and 13C NMR spectroscopy as well. The crystal structure of 4 has been determined by an X-ray diffraction study. The crystal data and the final R values are as follows: space group P 1 ( Z = 1) with cell parameters a = 9.060(7) Å, b = 9.126(9) Å, α = 9.723(6) Å, α = 107.46(4)°, β = 91.20(4)°, γ = 116.23(3)°, R = 0.041, R w = 0.050. The structural details are discussed. The first results of the reaction of 2 with CO are described, and IR investigation of the reaction mixture suggest that carbonyl cluster dianions of the composition [Pd 3(CO) 3(μ 2-CO) 3] n 2− are present in solution. Other products of this reaction are 1-butyleyclopentanol, cyclopentanone and cyclopentanol.