Analysis of the products of the anionic oligomerisation of a phosphaalkene using MALDI-TOF mass spectrometryElectronic supplementary information (ESI) available: experimental procedures and an additional figure. See http://www.rsc.org/suppdata/cc/b4/b406160h/

Abstract

The first use of MALDI-TOF MS in the study of the products of RLi (R = Me, Bu) initiated oligomerisation of P[double bond, length as m-dash]C bonds is reported. These studies may be considered as models for analogous polymerisation reactions. The detected linear products with R-P and C-H end-groups are consistent with a chain growth mechanism similar to that known for olefins. Interestingly, the results suggest that backbiting may compete with chain growth.

Ambient‐Temperature Living Anionic Polymerization of Phosphaalkenes: Homopolymers and Block Copolymers with Controlled Chain Lengths

“…Clearly, improved methods are necessary for the polymerization of 1 . It has been noted that 1 a reacts rapidly with alkyl lithium reagents (for example, MeLi) to afford MesP(Me)CPh 2 Li ( δ ( 31 P)=−45 ppm; Mes=2,4,6‐Me 3 C 6 H 2 )10, 12 which in the presence of additional 1 a forms short‐chain oligomers 13. Prompted by these observations, we speculated that the anionic polymerization of 1 may be living under the right conditions.…”

Macromolecular complexation of poly(methylenephosphine) to gold(i): a facile route to highly metallated polymers

“…We are tackling this problem by developing the addition polymerization of phosphaalkenes (PA) to afford homo-or co-polymers (Scheme 1). [3][4][5][6] The resultant polymers, called poly(methylenephosphine)s (PMP), are an unprecedented class of macromolecule which possess alternating phosphorus and carbon atoms.…”

Mass spectrometric characterization of oligomeric phosphaalkenes

“…Herein, we describe the analysis of oligomeric models for polymer 2 by using ESI-MS methods 29 , both with and without oxidation of the oligomeric products. The oligomers, 2 n , were prepared following the identical procedure to that described previously for the earlier MALDI-TOF analyses (Scheme 1) 25 . ESI-MS is a powerful tool for the examination of inorganic materials 30,31 .…”

“…Although these recent mechanistic investigations involved multinuclear one-and twodimensional NMR spectroscopy, we earlier studied the MALDI-TOF MS of oligomers derived from the anionic oligomerization of MesP=CPh 2 with MeLi or BuLi (25 mol%) 25 . Oligomerization of 1 (Scheme 1) leads to a mixture of oligomeric species (2 n ) that can be characterized by MALDI-TOF MS as the phosphine oxides (3 n ) after oxidation with H 2 O 2 .…”