Premium
Reaction of a Terminal Phosphinidene Complex with Azulenes: η 1 ‐Complexes, CH Bond Insertions, and 1,4‐Adducts
Author(s) -
Bulo Rosa E.,
Ehlers Andreas W.,
de Kanter Frans J. J.,
Schakel Marius,
Lutz Martin,
Spek Anthony L.,
Lammertsma Koop,
Wang Bing
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305711
Subject(s) - phosphinidene , adduct , terminal (telecommunication) , chemistry , stereochemistry , photochemistry , organic chemistry , computer science , telecommunications
Reaction of an in situ generated phosphinidene complex [PhPW(CO) 5 ] with the aromatic azulene and guaiazulene leads to unexpected 1,4‐adducts of the seven‐membered ring and to CH bond insertion of the five‐membered ring. A DFT analysis suggests that the reaction is initiated by formation of a η 1 ‐complex between the phosphinidene and the five‐membered ring of the aromatic substrate. Four conformations of this complex were identified. Two convert without barrier to the slightly more stable syn‐ and anti ‐1,2‐adducts. These undergo pericyclic 1,7‐sigmatropic rearrangements with remarkably low barriers to give 1,4‐adducts, with an inverted configuration at the phosphorus center. An X‐ray crystal structure is presented for one of the 1,4‐adducts of guaiazulene. The other two η 1 ‐complexes insert with modest barriers into a CH bond of the five‐membered ring.