Reaction of a complexed phosphinidene with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene.
The terminal phosphinidene complex PhPW(CO)5 reacts with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene to give two unexpected multicyclic organophosphorus compounds. One of them results from an initial 1,2-addition, followed by an intramolecular rearrangement. B3LYP/6-31G* calculations on simplified parent systems suggest that the reaction follows a unique concerted reaction pathway. The second, and major, product is a tetraphosphaquadricyclane derivative, which presumably results from an intramolecular [2+2] cycloaddition of an intermediate tetraphosphanorbornadiene complex. Single-crystal X-ray structures are presented for both products.
Vlaar
M J
MJ
Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, Amsterdam, The Netherlands.
Ehlers
A W
AW
Schakel
M
M
Clendenning
S B
SB
Nixon
J F
JF
Lutz
M
M
Spek
A L
AL
Lammertsma
K
K