Abstract
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 language | English |
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Pages (from-to) | 2080-2090 |
Number of pages | 11 |
Journal | Organometallics |
Volume | 39 |
Issue number | 11 |
DOIs | |
Publication status | Published - 8 Jun 2020 |
Equipment
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Australian Synchrotron
Office of the Vice-Provost (Research and Research Infrastructure)Facility/equipment: Facility
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X-ray Platform (MXP)
James Griffith (Manager)
Office of the Vice-Provost (Research and Research Infrastructure)Facility/equipment: Facility