Synthesis, reactivity and characterization of cyclometallated palladium(II) compounds derived from pinacolone-N,N-dimethylhydrazone
作者:José M Vila、Margarita López-Torres、Alberto Fernández、M.Teresa Pereira、Juna M Ortigueira、Jesús J Fernández
DOI:10.1016/s0020-1693(02)01146-5
日期:2003.1
Pinacolone-N,N-dimethylhydrazone was regiospecifically cyclopalladated by Pd(OAc)(2) in glacial acetic acid on the -C(Me)=N-methyl group to give the acetato-bridged complex [PdCH2C(CMe3)=NNMe2}(mu-O2CMe)](2) (1). Subsequent treatment with aqueous sodium chloride or bromide gave the corresponding halide-bridged complexes [Pd CH2C(CMe3) =NNMe2} (mu-X)](2) (2, X = Cl; 3, X = Br). Treatment of 2 and 3 with tertiary diphosphines in a 1: 1 molar ratio yielded the dinuclear complexes [Pd[CH2C(CMe3)=NNMe2](X)}(2)mu-Ph2PRPPh2}] (4, 5, R = CH2; 6, 7, R = CHMe; 8, 9, R = CCH2; 10, 11, R = NMe; 12, 13, R = trans-CHCH, 14, 15, R = C2H4, 16, 17, R = C3H6; 18, 19, R = C4H8). Treatment of 2 and 3 with AgClO4 and the appropriate diphosphine ligand in a 1:2 molar ratio, afforded the mononuclear species [PdCH2C(CMe3)=NNMe2)(Ph2PRPPh2-P,P')][ClO4]}] (20, R = CH2; 21, R = CHMe; 22, R = CCH2; 23, R = NMe; 24, R = cis-CHCH, 25, R = C2H2, 26, R = C3H6; 27, R = C4H8). The complexes were characterized by elemental analysis (C, H, N), conductivity measurements, IR and H-1 and (31)p H-1} NMR spectroscopy, and by mass spectrometry. (C) 2002 Elsevier Science B.V. All rights reserved.