Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 58, Pages 15669-15677Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201803477
Keywords
anilines; dialkylphenyphosphines; metallation; regioselectivity; synergistic effect
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Funding
- Australian Research Council [DE140101137]
- Monash University
- Australian Government Research Training Program (RTP) Scholarship
- Alexander von Humboldt foundation
- Australian Research Council [DE140101137] Funding Source: Australian Research Council
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A series of dialkylphenylphosphines and their analogous aniline substrates have been metallated with the synergistic mixed-metal base [(TMEDA)Na(TMP)(CH2SiMe3)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)(CH2PCH3Ph)Mg(TMP)]2, [(TMEDA)Na(TMP)(m-C(6)H(4)PiPr(2))Mg(TMP)]3 and [(TMEDA)Na(TMP)(m-C6H4NEt2)Mg(TMP)] 4 and two homometallic complexes [{(TMEDA)Na(EtNC6H5)}(2)]5 and [(TMEDA)Na-2(TMP)(C6H5PEt)](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.
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