| Abstract |
Refluxing PdCl2 with the ketoximes (RRC)-R-1-C-2=NOH ((RR2)-R-1 = MeMe, MeEt, C5H10) in RCN (R = Me, Et, nPr, Ph) for 2-3 h results in precipitation of the oxime complexes [PdCl2((RRC)-R-1-C-2=NOH)(2)], whereas further reflux of the reaction mixture for an additional 6-12 h leads to formation of the chelated species [PdCl2\NH=C(R)ON=(CRR2)-R-1-kappa(2)N\] (R/(RR2)-R-1 = Me/MeMe 1; Et/MeMe 2; nPr/MeMe 3; Me/MeEt 4; Me/C5H10 5; Ph/MeMe 6) by a P-II-mediated coupling between the oximes and the nitriles; complexes 1-6 were isolated in the solid state in 60-75 \% yields. The reaction time could be drastically reduced, to 15-30 min, when the system was additionally irradiated with microwaves (100 W, about 60 degrees C). Compounds 1-6 can also be obtained without isolation of the intermediate oxime complexes either by refluxing for 8-15 h or by microwave irradiation (100 W, about 60 degrees C) for 15-30 min. The formulation of 1-6 is based upon satisfactory C, H, and N elemental analyses, FAB mass spectrometry, and IR, H-1 and C-13\H-1\ NMR spectroscopy, while the structures of 1(.)(Me2CO), 1(.)(CHCl3), 2(.)(H2O), and 6(.1)/(2)(H2O) were determined by X-ray single-crystal diffraction. ((c) Wiley-VCH Verlag GmbH \& Co. KGaA, 69451 Weinheim, Germany, 2005). |
