Synthesis, Structure, and Solution Studies of Lithiated Allylic Phosphines and Phosphine Oxides

Nimrod M. Eren, Samantha A. Orr, Christopher D. Thompson, Emily C. Border, Michael A. Stevens, Victoria L. Blair

Research output: Contribution to journalArticleResearchpeer-review


This study reports a new series of 12 α-lithiated allylic phosphines and phosphine oxides. By incorporating Lewis base donors including diethyl ether (Et2O), tetrahydrofuran (THF), N,N,N′,N′,-tetramethylethylenediamine (TMEDA), and N,N,N′,N′,N″,-pentamethyldiethylenetriamine (PMDETA), nine complexes were structurally characterized by single-crystal X-ray crystallography. This includes novel dilithiated allylic phosphine 4 [PhP{CHCHCH2Li(TMEDA)}2] and a rare hemisolvated lithiated phosphine oxide 6 [{Ph2P(O)CHC(Me)CH2Li}2(TMEDA)]. Interestingly, in the solid state, P(III) complexes take advantage of Li-πinteractions to the newly formed delocalized system, in comparison to P(V) complexes where the oxophillic nature of the lithium atom dominates. All 12 complexes were fully characterized in the solution state by multinuclear NMR spectroscopy. DFT calculations on isomers of monomeric lithiated complex 3 [Ph2PCHC(Me)CH2Li(PMDETA)] described the low energy barrier between transition steps of the subtle delocalization of the allylic chain.

Original languageEnglish
Pages (from-to)2080-2090
Number of pages11
Issue number11
Publication statusPublished - 8 Jun 2020

Cite this