Palladium(II) saccharinate complexes trans-[Pd(sac)2(LH)2] with amino- and acetylamino-pyridine co-ligands: molecular structures of trans-[PdCl2(2-ampyH)2].2dmf (2-ampyH = 2-amino-3-methylpyridine) and trans-[Pd(κ2-2-acmpy)2] (2-acmpyH = 2-acetylamino-3-methylpyridine) (original) (raw)
2014, Transition Metal Chemistry
Palladium(II) saccharinate (sac) and thiosaccharinate (tsac) complexes with 2-aminopyridine (2-ampy), 2-acetylaminopyridine (2-aampy) and 2-acetylaminopyrimidine (2-aampym) co-ligands: X-ray crystal structures of trans-[Pd(sac) 2 (ampy) 2 ] and solvatomorphs trans-[Pd(sac) 2 (2-aampy) 2 ]ÁS (S = CHCl 3 , thf) a b s t r a c t Reactions of Na 2 PdCl 4 with two equivalents of 2-aminopyridine (2-ampy), 2-acetylaminopyridine (2aampy) or 2-acetylaminopyrimidine (2-aampym) afford complexes of the type trans-[PdCl 2 L 2 ]. Further reaction with two equivalents of sodium saccharinate (Nasac) affords mixed-ligand complexes trans-[Pd(sac) 2 L 2 ]. X-ray structures of trans-[Pd(sac) 2 (2-ampy) 2 ] and two solvatomorphs of trans-[Pd(sac) 2 (2aampy) 2 ].S (S = CHCl 3 , thf) have been carried out. In all three, the saccharinate ligands coordinate in a monodentate fashion via the endocyclic amido group and all four ligands lie approximately perpendicular to the PdN 4 plane. In trans-[Pd(sac) 2 (2-ampy) 2 ] the metal ion lies on an inversion centre and consequently the ligands adopt a relative anti/anti-configuration, while in both solvatomorphs of trans-[Pd(sac) 2 (2-aampy) 2 ] they adopt a syn/syn-configuration, the latter possibly resulting from intramolecular hydrogen bonding between the amine protons and the carbonyl oxygen. Reactions of trans-[PdCl 2 L 2 ] with thiosaccharin (tsacH) are dependent upon the nature of the amine. Thus, with trans-[PdCl 2 (2ampy) 2 ] the desired mixed-ligand complex trans-[Pd(tsac) 2 (2-ampy) 2 ] results, however with acetylamine complexes only the known homoleptic complex, [Pd(tsac) 2 ], is isolated.
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