The cyclotetramerisation of dimethyl acetylenedicarboxylate and the x-ray structure of [pd{h(c8(co2me)8)}cl(pyridine)2], an unusual five-co-ordinate palladium(ii) complex

Konietzny, Alfred; Bailey, Pamela M.; Maitlis, Peter M.

doi:10.1039/c39750000078

Cited by 13 publications

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“…A number of other Pd(II)-induced reactions also give substituted cyclopentadienes, for example, vinylpentamethylcyclopentadiene (9) from 2-butyne, and 10 from dimethyl acetylenedicarboxylate. 20 The complex 11, containing the pentaphenylcyclopentadienyl ligand, has also Palladium(II) Induced Oligomerization of Acetylenes been isolated from reactions of diphenylacetylene under appropriate conditions.21 (d) Evidence concerning precursors to the trimer complexes comes from a variety of reactions. For example, in a study of the reactions of the zerovalent palladium-olefin tt complexes Pd(DBA)M [DBA = dibenzylideneacetone]22 with dimethyl acetylenedicarboxylate, the first product was identified as the metallocycle 12.23 This also reacts further to give the benzene 6 by a different path from the one under discussion here, but one which has been well established for electrophilic acetylenes and low-oxidation-state metal complexes.…”

Section: Fragmentarymentioning

confidence: 99%

The palladium(II)-induced oligomerization of acetylenes: an organometallic detective story

Maitlis¹

1976

Acc. Chem. Res.

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180

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One of the most fascinating chapters in organometallic chemistry concerns the interaction of transition-metal compounds with acetylenes. The number of different strange, unusual, and apparently unrelated types of molecules isolated from these reactions reminds one of the early days of organic natural product chemistry; the tale of the unravelling of their structures and of the elucidation of apparently tortuous mechanisms by which they are formed is reminiscent of a detective story. Clues abound, there are many red herrings, and the answer to the puzzle is seldom obvious even halfway through the problem.Interest in the general area was dramatically awakened by Reppe's discovery of the tetramerization of acetylene to cyclooctatetraene by a nickel catalyst.1 This was followed by extensive investigations of the structures of the multitude of complexes isolated from reactions of metal carbonyls and acetylenes, particularly by Hübel and his co-workers,2 and many others. These studies showed that a number of complex processes occur during such reactions, many involving polynuclear intermediates, and even today our understanding of that particular story is only

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Section: Fragmentarymentioning

confidence: 99%