A series of dialkylphenylphosphines and their analogous aniline substrates have been metallated with the synergistic mixed-metal base [(TMEDA)Na(TMP)(CH2 SiMe3 )Mg(TMP)] 1. Different metallation regioselectivities for the substrates were observed, with predominately lateral or meta-magnesiated products isolated from solution. Three novel heterobimetallic complexes [(TMEDA)Na(TMP)(CH2 PCH3 Ph)Mg(TMP)] 2, [(TMEDA)Na(TMP)(m-C6 H4 PiPr2 )Mg(TMP)] 3 and [(TMEDA)Na(TMP)(m-C6 H4 NEt2 )Mg(TMP)] 4 and two homometallic complexes [{(TMEDA)Na(EtNC6 H5 )}2 ] 5 and [(TMEDA)Na2 (TMP)(C6 H5 PEt)]2 6 derived from homometallic metallation have been crystallographically characterised. Complex 6 is an unprecedented sodium-amide, sodium-phosphide hybrid with a rare (NaNNaP)2 ladder motif. These products reveal contrasting heterobimetallic deprotonation with homometallic induced ethene elimination reactivity. Solution studies of metallation mixtures and electrophilic iodine quenching reactions confirmed the metallation sites. In an attempt to rationalise the regioselectivity of the magnesiation reactions the C-H acidities of the six substrates were determined in THF solution using DFT calculations employing the M06-2X functional and cc-pVTZ Dunning's basis set.
Keywords: anilines; dialkylphenyphosphines; metallation; regioselectivity; synergistic effect.
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