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Unexpected Oxidative Dimerisations of a Cyclopentadienyl‐Phosphane – Formation of Unprecedented, Structurally Remarkable Phosphacyclic Compounds
Author(s) -
Lichtenberg Crispin,
Elfferding Michael,
Sundermeyer Jörg
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200901267
Subject(s) - chemistry , diiodomethane , phosphonium , electrophile , cyclopentadienyl complex , ionic bonding , medicinal chemistry , oxidative addition , counterion , photochemistry , organic chemistry , ion , catalysis , surface energy
The reactions of Me 2 PCp # ( 1 ) (Cp # = C 5 HMe 4 ) with Ph 3 PCH 2 X + X – (X = Cl, Br, I) and diiodomethane as potential electrophiles have been investigated. Unexpectedly, in all four cases unprecedented oxidative dimerisations of the cyclopentadienylphosphane 1 have been observed. In the reactions with the phosphonium salts, an ionic group 15 analogue of octamethyl‐tetrahydro‐ s ‐indacene with different counterions X – has been obtained ( 5 – 7 ) as a result of X + transfer and H + elimination. In the reaction of 1 with diiodomethane a fourfold anellated, partially unsaturated, heterocyclic compound 9 exhibiting two spiro carbon centres, which are directly linked, was formed, presumably as a result of iodine radical transfer. Both of the novel phosphorus heterocycles have been characterised by means of single crystal XRD analysis.