ISSN:
1434-1948
Schlagwort(e):
Palladium
;
Tripodal ligands
;
O ligands
;
Fluxionality
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The reaction of [PdCl2(CH3CN)2] with the silver salt of the tripodal oxygen ligand L- = [(C5H5)Co{P(O)(OMe)2)}3]- yields the homoleptic oxygen ligand complex [PdL2] (1). The molecular structure of 1 was determined by single-crystal X-ray diffraction: monoclinic space group P21/n; a = 8.515(1), b = 13.627(2), c = 15.828(2) Å; β = 92.44(1)°; V = 1834.9(7) Å3; Z = 2. The complexes [Pd(PPh3)XL] [X = Cl (2a), Br (2b), I (2c)] have been prepared starting from 1. Complex 2a reacts with PPh3 to form [Pd(PPh3)2L]Cl (3a) and [Pd(PPh3)2L]L (3b). Treatment of 2a with CO in MeOH yields the carboxymethyl complex [{(PPh3)(COOMe)Pd(μ-Cl)}2] (4) and the protonated ligand HL. The carboxymethyl complex 4 shows some catalytic activity for the copolymerization of CO and ethene. Complex 4 reacts with AgL to yield [Pd(PPh3)(COOMe)L] (6). Alkylation of 2a with Me4Sn leads to the methyl complexes [Pd(PPh3)MeL] (7) and [Me2ClSnL] (8). CO insertion in the palladium-carbon bond of 7 gives the stable acetyl complex [Pd(PPh3){C(O)Me}L] (10). The palladium(II) complexes 1, 2, 3, 6, 7, and 10 of the tripodal oxygen ligand L are all fluxional molecules that have been studied by temperature-dependent 1H- and 31P-NMR spectroscopy.
Zusätzliches Material:
5 Ill.
Materialart:
Digitale Medien
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