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Palladium(II) complexes of diphenylvinyl- and phenyldivinylphosphine

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00281a003· OSTI ID:5826130
Palladium(II) complexes of the ligands L = Ph/sub 2/PCH/double bond/CH/sub 2/ and PhP(CH/double bond/CH/sub 2/)/sub 2/ have been prepared and characterized by elemental analysis, infrared spectroscopy, and /sup 1/H, /sup 1/H(/sup 31/P), /sup 13/C(/sup 1/H), /sup 31/P(/sup 1/H), and /sup 1/H//sup 13/C HETCOR nuclear magnetic resonance spectroscopy. These complexes exist as temperature-dependent equilibrium mixtures of cis and trans isomers in solution. Equilibrium thermodynamics for the isomerization process cis-L/sub 2/PdX/sub 2/ /rightleftharpoons/ trans-L/sub 2/PdX/sub 2/, determined by variable-temperature /sup 31/P(/sup 1/H) NMR spectroscopy, demonstrate that the cis isomers are in general thermodynamically more stable than the trans isomers. However, the relatively isomer stabilities are anion dependent with the trans isomer becoming more stable in the order Cl < Br < I. Coordination of a vinylphosphine to palladium(II) strongly polarizes the C/double bond/C double bond as evidenced by /sup 13/C NMR data. 27 refs., 2 figs., 4 tabs.
Research Organization:
Univ. of Nevada, Reno (USA)
OSTI ID:
5826130
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:8; ISSN INOCA
Country of Publication:
United States
Language:
English