13444-94-5Relevant articles and documents
Smith, E. F.,Wallace, D. L.
, p. 465 - 465 (1894)
Preparation, magnetic properties, and pressure-induced transitions of some MIIMIVF6 (MII = Ni, Pd, Cu; MIV = Pd, Pt, Sn) complex fluorides
Tressaud,Bartlett
, p. 333 - 340 (2001)
MIIMIVF6 (MII = Ni, Pd, Cu; MIV = Pd, Pt) and PdSnF6 complex fluorides have been synthesized via different preparative methods using either BrF3 as oxidizer and solvent, or solid state reactions. For MII = Ni, Pd, the phases crystallize in the rhombohedral space group R3 (LiSbF6 type). Cationic ordering has been studied by X-ray diffraction and 119Sn Moessbauer resonance for PdSnF6. A lowering of symmetry has been observed when the involved divalent cation presents a Jahn-Teller configuration (CuII). Except for PdSnF6, which is paramagnetic down to 4 K, all compounds are Pd2F6-type ferromagnets at low temperature. This behavior has been related to the ordering between half-filled eg orbitals of the divalent cation and empty eg orbitals of the tetravalent cation. A drastic increase in conductivity has been observed under high pressures. In particular the insulator-semiconductor transition induced under pressure (up to 80 kbar) in Pd2F6 corresponds to a decrease of the electrical resistivity by six orders of magnitude. The assumption of an electronic transition induced under pressure from mixed oxidation states (MII + MIV) to an unique trivalent MIII oxidation state has been proposed.
Ortho palladation and functionalization of L-phenylalanine methyl ester
Vicente, Jose,Saura-Llamas, Isabel,Garcia-Lopez, Jose-Antonio,Calmuschi-Cula, Beatrice,Bautista, Delia
, p. 2768 - 2776 (2007)
The ortho-metalated complex (S,S)-[Pd2{κ2(C,N)- C6H4CH2CH(CO2Me)NH 2-2}2(μ-Br)2] (1b) can be prepared by refluxing in acetonitrile equimolecular amounts of Pd(OAc)2 and L-phenylalanine methyl ester hydrochloride, followed by addition of an excess of NaBr. Complex 1b reacts with 4-picoline to give the mononuclear derivative (S)-[Pd{κ2(CN)-C6H4CH 2CH(CO2Me)NH2-2}2Br(NC 5H4Me-4)] (2), whose crystal structure has been determined by X-ray diffraction. The precursor of 1b, (S,S)- [Pd2{κ2-(C,N)-C6H4CH 2CH(CO2Me)NH2-2}2(μ-Cl) 2] (1a), could not be isolated in a pure form, but it can be used as the starting material for the synthesis of functionalized derivatives of the phenylalanine methyl ester. Thus, CO and RNC (R = Xy, tBu) insert into the Pd-C bond of 1a to afford, after depalladation, (S)-1-oxo-3- (methoxycarbonyl)-1,2,3,4-tetrahydroisoquinoline (3) and (S)-l-R-3- (methoxycarbonyl)-3,4-dihydroisoquinolinium triflate (R = tBu (4), Xy (5)), respectively. Reaction of complex 1b with bromine or iodine affords trans-(S,S)-[PdBr2{NH2CH(CO2Me)CH 2C6H4-X-2}2] (X = Br (6), I (7)), which further reacts with 1, 10-phenanthroline (phen) to give [PdBr 2(phen)] and (S)-2-X-phenylalanine methyl ester (X = Br (8). I (9)).
Co-ordination Chemistry of Higher Oxidation States. Part 3. Palladium(IV) Complexes with Neutral Unidentate Ligands
Gulliver, David J.,Levason, William
, p. 1895 - 1898 (2007/10/02)
Oxidation of with the corresponding halogen (X2) in carbon tetrachloride gave octahedral palladium(IV) anions n3, X=Cl; L=PEt2Ph, X=Br>.Attemps toprepare analogues with L=SbMe3, TeMe2, or dmso (dimethyl sulphoxide) failed.Neutral palladium (IV) complexes trans- (L=NMe3, Py, PPrn3, or AsMe2Ph, X= Cl; L=NMe3, X= Br) have been obtained from trans- and X2.The complexes were characterised by i.r. and electronic spectroscopy, and conductivity measurements, and their thermal decomposition examined by t.g.a.
