TY - JOUR
T1 - Reaction of a complexed phosphinidene with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene
AU - Vlaar, Mark J.M.
AU - Ehlers, Andreas W.
AU - Schakel, Marius
AU - Clendenning, Scott B.
AU - Nixon, John F.
AU - Lutz, Martin
AU - Spek, Anthony L.
AU - Lammertsma, Koop
PY - 2001/8/17
Y1 - 2001/8/17
N2 - 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.
AB - 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.
KW - Cycloaddition
KW - Density functional calculations
KW - Electrophilic aromatic substitution
KW - Phosphinidene complex
KW - Triphosphabenzene
UR - http://www.scopus.com/inward/record.url?scp=0035902861&partnerID=8YFLogxK
U2 - 10.1002/1521-3765(20010817)7:16<3545::AID-CHEM3545>3.0.CO;2-0
DO - 10.1002/1521-3765(20010817)7:16<3545::AID-CHEM3545>3.0.CO;2-0
M3 - Article
C2 - 11560325
AN - SCOPUS:0035902861
SN - 0947-6539
VL - 7
SP - 3545
EP - 3550
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 16
ER -