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Transition-metal-Carbon Bonds. Part 45. Attempts to Cyclopalladate Some Aliphatic Oximes, NN-Dimethylhydrazones, Ketazines, and Oxime O-Allyl Ethers. Crystal Structures of 2Cl2> and (acac)>

DOI: 10.1039/DT9800001992

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1992 - 2000 (1980)

Update date:2022-09-26

Topics:

Authors:

Constable, Anthony G.Constable, Anthony G.

McDonald, Walter S.McDonald, Walter S.

Sawkins, Lynne C.Sawkins, Lynne C.

Shaw, Bernard L.Shaw, Bernard L.

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Article abstract of DOI:10.1039/DT9800001992

E-Methyl t-butyl ketoxime, with sodium acetate and Na2 in methanol, cyclopalladates regiospecifically on a t-butyl methyl to give the chloride-bridged complex 2Cl2> (1a), the crystal structure of which has been determined (see below).The corresponding bromide and iodide complexes have been made, as have several mononuclear species by bridge-splitting reactions, e.g. of type (X = Cl or Br; L = CO, PMe2Ph, PPh3, or pyridine).The salts (Ph2PCH2CH2PPh2)>X (X = I or BPh4) have also been prepared.E-Ethyl t-butyl and E-phenyl t-butyl ketoximes are similarly cyclopalladated, but oximes of other carbonyl compounds, e.g. trimethylacetaldehyde, methyl isopropyl ketone, diisopropyl ketone, ethyl methyl ketone, or 2-methylcyclohexanone, give dark intractable products. In contrast, methyl t-butyl NN-dimethylhydrazone with Na2 and Na cyclometallates regiospecifically on the single methyl group to give t>2Cl2>.The corresponding bromide or iodide complexes have been made as have bridge-split derivatives (with PMe2Ph, PPh3, or pyridine) and also an acetylacetonate, (acac)> (6), the crystal structure of which has been determined. NN-dimethylhydrazones of acetaldehyde, acetone, cyclohexanone, or 4-t-butylcyclohexanone cause decomposition on attempted cyclopalladation. Acetophenone NN-dimethylhydrazone cyclopalladates specifically on the 2 position of the benzene ring (i.e.not on the C-methyl group). Methyl t-butylketazine cyclopalladates specifically on a t-butyl methyl giving t)CH3>2Cl2>: dimetallation could not be effected.Acetoxime O-allyl ether in methanol is cyclopalladated with concomitant attack by OMe to give .The corresponding ethoxy-compound is formed in ethanol: cyclohexanone oxime O-allyl ether is similarly palladated.Crystal data are: (1a), Monoclinic, space group P21/c, a = 7.312(1), b = 8.539(2), c = 28.478(4) Angstroem, β = 91.74(1) deg, and Z = 4; (6), Triclinic, space group PI, a = 9.573(3), b = 10.714(3), c = 8.983(2) Angstroem, α = 94.41(2), β = 113.76(2), γ = 104.65(2) deg, and Z = 2.

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Cas No:76046-72-5

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