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Tripodal Oxygen Ligand Supported Palladium(II) Complexes: Alkylation, Carboxymethylation, and CO Insertion Reactions – X-ray Crystal Structure Determination of [PdL2], L– = [(C5H5)Co{P(O)(OMe)2}3]–, a Novel Homoleptic Oxygen Ligand Palladium Complex

✍ Scribed by Wolfgang Kläui; Marcus Glaum; Ekkehardt Hahn; Thomas Lügger


Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
376 KB
Volume
2000
Category
Article
ISSN
1434-1948

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✦ Synopsis


Palladium / Tripodal ligands / O ligands / Fluxionality The reaction of [PdCl 2 (CH 3 CN) 2 ] with the silver salt of the ligand HL. The carboxymethyl complex 4 shows some catalytic activity for the copolymerization of CO and ethene. tripodal oxygen ligand L -= [(C 5 H 5 )Co{P(O)(OMe) 2 )} 3 ] -yields the homoleptic oxygen ligand complex [PdL 2 ] (1). The Complex 4 reacts with AgL to yield [Pd(PPh 3 )(COOMe)L] (6). Alkylation of 2a with Me 4 Sn leads to the methyl complexes molecular structure of 1 was determined by single-crystal Xray diffraction: monoclinic space group P2 1 /n; a = 8.515(1), [Pd(PPh 3 )MeL] (7) and [Me 2 ClSnL] (8). CO insertion in the palladium-carbon bond of 7 gives the stable acetyl complex b = 13.627(2), c = 15.828(2) A ˚; β = 92.44(1)°; V = 1834.9(7) A ˚3; Z = 2. The complexes [Pd(PPh 3 )XL] [X = Cl (2a), Br (2b), I [Pd(PPh 3 ){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 (2c)] have been prepared starting from 1. Complex 2a reacts with PPh 3 to form [Pd(PPh 3 ) 2 L]Cl (3a) and [Pd(PPh 3 ) 2 L]L (3b).

molecules that have been studied by temperature-dependent 1 H-and 31 P-NMR spectroscopy. Treatment of 2a with CO in MeOH yields the carboxymethyl complex [{(PPh 3 )(COOMe)Pd(µ-Cl)} 2 ] (4) and the protonated involve a change of the palladium oxidation state from II [a] Institut für Anorganische Chemie und Strukturchemie der Uniplexes with hard oxygen donors are rarely observed.