135484-02-5Relevant articles and documents
A Simple Method for the Preparation of Alkylpalladium Compounds by Pd-O Bond Cleavage in Cationic Bis(ether-phosphane)palladium(II) Complexes with Grignard Reagents
Lindner, Ekkehard,Dettinger, Johannes,Fawzi, Riad,Steimann, Manfred
, p. 1347 - 1354 (2007/10/02)
The bis(chelate) complexes O)2>2 (3a-e) react with methylmagnesium chloride with a concomitant cleavage of two weak Pd-O bonds to give the methyl complexes trans-ClPd(PO)2(CH3) (4a-e) (PO: η1-P-coordinated; PO: η2-O,P-chelated; Scheme 1).Diffusion of pentane into the reaction mixture of 4a-e in the presence of the formed magnesium salts yields the cationic complexes trans-O)-(PO)> (6a, c).The reaction of 3a-e with benzylmagnesium chloride affords the cationic benzyl complexes cis-O)(PO)> (8a-e) inwhich only one Pd-O bond has been cleaved.In the presence of carbon monoxide 4a-e and 6a, c are transformed into the corresponding acyl complexes CH3C(O)Pd(PO)2Cl (5a-e) and O)(PO)> (7a, c).Whereas at 183 K variable-temperature 31P-NMR measurements of 6a, c, 7a, c indicate a non-rigid behavior of the two differently bound ether-phosphanes, the dynamic process is frozen out for 8a-e.By a line-shape analysis of the spectra the thermodynamic parameters ΔG(excit.), ΔH(excit.), and ΔS(excit.) are obtained.According to a crystal structure analysis 3d and 6c crystallize in the monoclinic space group P21/c with Z = 4.Key Words: Palladium complexes, alkyl- and acyl- / Ether phosphanes / Fluxional behavior