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CC Bond Insertion of a Complexed Phosphinidene into 1,6‐Methano[10]annulene
Author(s) -
Bulo Rosa E.,
Trion Linda,
Ehlers Andreas W.,
de Kanter Fransiscus J. J.,
Schakel Marius,
Lutz Martin,
Spek Anthony L.,
Lammertsma Koop
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.200400519
Subject(s) - phosphinidene , annulene , chemistry , intramolecular force , stereochemistry , ring (chemistry) , triple bond , crystallography , double bond , polymer chemistry , organic chemistry
Reaction of electrophilic phosphinidene complex [MePW(CO) 5 ] with 1,6‐methano‐[10]annulene results in the sole formation of the isomeric CC insertion products 6 c (main) and 6 d (minor). The single‐crystal X‐ray structure of the complexed 1,7‐methano‐3‐phospha[11]annulene ( 6 c ) shows a syn‐ W(CO) 5 group at the exo bent phosphorus. The structure displays CC bond alternation without bonding between the bridgehead carbon atoms. Density functional theory calculations indicate 6 c to result from a concerted disrotatory ring opening of an undetected tricyclic exo – syn phosphirane intermediate. The endo – anti phosphirane cannot undergo ring expansion, due to the high barrier that is associated with an intramolecular antara–antara retro Diels–Alder reaction. The stabilizing effect of transition‐metal coordination is discussed.