Palladium(II) complexes with 2-acetylamino-5-mercapto-1,3,4-thiadiazolate (amta) ligands: Molecular structures of the all trans dipalladium “paddlewheel” Pd2(μ-amta)4 and Pd(κ1-amta)2(κ2-dppe) (original) (raw)
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Inorg Chim Acta, 2006
The reaction of [PdCl2(CH3CN)2] with N-alkylaminopyrazole (NN′) ligands, 1-[2-(ethylamino)ethyl]-3,5-dimethylpyrazole (deae), 1-[2-(ipropylamino)ethyl]-3,5-dimethylpyrazole (deai), and 1-[2-(tbutylamino)ethyl]-3,5-dimethylpyrazole (deat), affords a series of square planar Pd(II) complexes [PdCl2(NN′)] (NN′ = deae (1), deai (2) and deat (3)). The solid-state structures of complexes 1 and 3 were determined by single crystal X-ray diffraction studies. The NN′ ligands are coordinated through the Npz and Namine atoms to the metal atom, which completes its coordination with two chlorine atoms in a cis disposition. These palladium(II) compounds were characterised by elemental analyses, conductivity measurements, IR, 1H and 13C{1H} NMR spectroscopies. The NMR studies of the complexes prove the rigid conformation of the ligands when they are complexed.The reaction of [PdCl2(CH3CN)2] with N-alkylamino pyrazole (NN′) ligands, 1-[2-(ethylamino)ethyl]-3,5-dimethylpyrazole (deae), 1-[2-(ipropylamino)ethyl]-3,5-dimethylpyrazole (deai), and 1-[2-(tbutylamino)ethyl]-3,5-dimethylpyrazole (deat), affords a series of square planar Pd(II) complexes [PdCl2(NN′)](NN′ = deae (1), deai (2), and deat (3)). The solid-state structures of complexes 1 and 3 were determined by single crystal X-ray diffraction studies. The palladium(II) compounds were characterised by elemental analyses, conductivity measurements, IR, 1H and 13C{1H} NMR spectroscopies. The NMR studies of the complexes prove the rigid conformation of the ligands when they are complexed.
European Journal of Inorganic Chemistry, 2006
Treatment of the tetradentate (NN 0 N 0 N) N-alkylaminopyrazole ligands 3,6-dimethyl-1,8-(3,5-dimethyl-1-pyrazolyl)-3,6-diazaoctane (ddad) and 1,4-bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]piperazine (bedp) with [PdCl 2 (CH 3 CN) 2 ] in a 1:1 M/L ratio in acetonitrile produces [Pd 2 Cl 4 (L)] and [PdCl 2 (L)] (L = ddad and bedp). Treatment of the corresponding complex [PdCl 2 (L)] (L = ddad, bedp) in the presence of AgBF 4 in CH 2 Cl 2 /methanol (2:1) or NaBF 4 in acetonitrile gives [Pd(L)](BF 4 ) 2 . The Pd(II) complexes have been characterised by elemental analyses, conductivity measurements, IR and 1 H and 13 C{ 1 H} NMR spectroscopies when possible. The X-ray structure of the complex [Pd(ddad)]Cl 2 Á 3H 2 O has been determined. The Pd(II) is coordinated to the ddad ligand by two nitrogen atoms of pyrazolyl groups and two nitrogen atoms of the amine groups, in a slightly distorted square-planar geometry.
Transition Metal Chemistry, 2014
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.
Transition Metal Chemistry, 2002
Mononuclear palladium(II) complexes containing both pyrazole-type ligands and thiocyanate, of general formula [Pd(SCN)2(L)2] {L = pyrazole (HPz) and 1-phenyl-3-methylpyrazole (phmPz)} have been prepared and characterized by elemental analysis, i.r. and n.m.r. spectroscopy and by single crystal X-ray diffraction methods. The Pd atom in these structures lies on the crystallographic inversion center; in a square-planar coordination geometry made by two sulfur and two nitrogen atoms of the ligands, both in trans positions.
a b s t r a c t The reaction of equimolar proportions of Na 2 [PdCl 4 ] and 1-(4-methylimidazol-5-yl) phenylhydrazono-propane-2-one oxime (LH), a 1:1 Schiff-base condensate of 1-hydrazono-1-phenyl-propan-2-one oxime (1) and 4-methylimidazole-5-carboxaldehyde, in methanol gives rise to [Pd(L)(Cl)] (2) in a satisfactory yield. The title monomeric palladium(II) complex, 2, has been characterized by C, H and N microanalyses, 1 H and 13 C NMR, FAB-MS, FT-IR, UV–Vis spectra, molar electric conductivity measurements and room temperature magnetic susceptibility measurements. The X-ray crystal structures of 1 and 2 have been determined. The structure of 1, a precursor of the ligand (LH), shows that the methyl and phenyl groups are in an 'anti' disposition. Compound 1 crystallizes in the monoclinic space group P2 1 with a = 6.9503(5), b = 6.4535(3), c = 10.1631(6) Å, V = 455.04(5) Å 3 and Z = 2. The structure of 2 reveals that it is a distorted square-planar palladium(II) compound. Th...
Journal of Organometallic Chemistry, 2015
Two new N-pyrazole, P-phosphine hybrids ligands: 1-[2-(diphenylphosphanyl)methyl]-3,5-dimethyl pyrazole (LP1) and 1-[2-(diphenylphosphanyl)propyl]-3,5-dimethylpyrazole (LP3) are presented. The reaction of these two ligands and two other ligands reported in the literature: 1-[2-(diphenylphosphanyl) ethyl]-3,5-dimethylpyrazole (LP2) and 1-[2-(diphenylphosphanyl)ethyl]-3,5-diphenylpyrazole (LP4) with [PdCl2(CH3CN)2] yield [PdCl2(LP)] (LP ¼ LP1 (1), LP2 (2), LP3 (3) and LP4 (4)) complexes. All complexes are fully characterised by analytical and spectroscopic methods and the resolution of the crystal structure of complexes 2 and 3 by single crystal X-ray diffraction is also presented. In these complexes the ligands are coordinated to Pd(II) via k2(N,P) forming metallocycles of six (2) and seven (3) members and finish their coordination with two cis-chlorine atoms. Finally, complex 2 is studied in the palladium-catalysed CeC coupling reaction, being active even for aryl chlorides substrates.