4.6 Article

Contrasting Synergistic Heterobimetallic (Na-Mg) and Homometallic (Na or Mg) Bases in Metallation Reactions of Dialkylphenylphosphines and Dialkylanilines: Lateral versus Ring Selectivities

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 58, Pages 15669-15677

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201803477

Keywords

anilines; dialkylphenyphosphines; metallation; regioselectivity; synergistic effect

Funding

  1. Australian Research Council [DE140101137]
  2. Monash University
  3. Australian Government Research Training Program (RTP) Scholarship
  4. Alexander von Humboldt foundation
  5. Australian Research Council [DE140101137] Funding Source: Australian Research Council

Ask authors/readers for more resources

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.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.6
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

No Data Available
No Data Available