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Synthesis and Thermal Decomposition of Palladacyclopentane Derivatives of the Type (R=H or Me). X-Ray Crystal Structure of

DOI: 10.1039/DT9880000133

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 133 - 140 (1988)

Update date:2022-08-28

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Authors:

Diversi, PietroDiversi, Pietro

Ingrosso, GiovanniIngrosso, Giovanni

Lucherini, AntonioLucherini, Antonio

Lumini, TitoLumini, Tito

Marchetti, FabioMarchetti, Fabio

et al.et al.

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Article abstract of DOI:10.1039/DT9880000133

A series of new palladacyclopentane derivatives of formula has been prepared.The first X-ray crystal structure determination of a palladacyclopentane derivative is reported: the compound gives crystals belonging to the C2/c space group: a=16.643(9), b=11.174(4), c=7.451(3) Angstroem, β=116.05(9) deg, and Z=4; R=0.0340 for 826 observed reflexions.The metal co-ordination is square planar and the molecules lie on a two-fold axis.The palladacyclopentane ring shows a half-chair conformation with the two-fold axis running through Pd and the middle of the C(β)-C(β') bond.A study of the thermal decomposition of the palladacyclopentanes has been carried out: (L=PPh3; L2=dppe, tmen, bipy, dcpe, or dppb) gives butenes as the major products; cyclobutane (L=PPh3) and ethylene (L2=dppe or dcpe) are also formed as minor products.By comparing these results with those for the decomposition of some methyl-substituted palladacyclopentanes, it is shown that the presence of ethylene is not attributable to fragmentation of the metallacyclic skeleton, but rather to the rupture of the P-C bonds of the diphosphine ligands.The decomposition of palladacyclopentanes is also induced by Bun2O*BF3: linear C4 hydrocarbons are formed.

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