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Metal‐Free Addition/Head‐to‐Tail Polymerization of Transient Phosphinoboranes, RPH‐BH 2 : A Route to Poly(alkylphosphinoboranes)
Author(s) -
Marquardt Christian,
Jurca Titel,
Schwan KarlChristian,
Stauber Andreas,
Virovets Alexander V.,
Whittell George R.,
Manners Ian,
Scheer Manfred
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201507084
Subject(s) - polymerization , monomer , catalysis , polymer chemistry , molar mass , thermal decomposition , metal , chemistry , base (topology) , materials science , polymer , organic chemistry , mathematical analysis , mathematics
Abstract Mild thermolysis of Lewis base stabilized phosphinoborane monomers R 1 R 2 PBH 2 ⋅NMe 3 (R 1 ,R 2 =H, Ph, or t Bu/H) at room temperature to 100 °C provides a convenient new route to oligo‐ and polyphosphinoboranes [R 1 R 2 P‐BH 2 ] n . The polymerization appears to proceed via the addition/head‐to‐tail polymerization of short‐lived free phosphinoborane monomers, R 1 R 2 P‐BH 2 . This method offers access to high molar mass materials, as exemplified by poly( tert ‐butylphosphinoborane), that are currently inaccessible using other routes (e.g. catalytic dehydrocoupling).