PlumX Metrics
Embed PlumX Metrics

Group 1 bis(iminophosphorano)methanides, part 2: N- aryl derivatives of the sterically demanding methanes HC(PPhNR) (R = 2,4,6-trimethylphenyl or 2,6-diisopropylphenyl)

Organometallics, ISSN: 0276-7333, Vol: 30, Issue: 20, Page: 5326-5337
2011
  • 24
    Citations
  • 0
    Usage
  • 19
    Captures
  • 0
    Mentions
  • 0
    Social Media
Metric Options:   Counts1 Year3 Year

Metrics Details

  • Citations
    24
    • Citation Indexes
      24
  • Captures
    19

Article Description

Treatment of HC(PPhNMes) (Mes = 2,4,6-trimethylphenyl) with 1 equiv of [Na(Bn)] (Bn = CHC H) in THF gave the Lewis base adduct [Na{HC(PPh NMes)}(THF)] (1). The heavy group 1 methanides [Rb{HC(PPhNMes)}(DME)] (2) and [Cs{HC(PPhNMes)}] (3) were prepared by the reaction of [MOR] (M = Cs, Rb; OR = 2-ethylhexoxide) with [Li{HC(PPh NMes)}]. The Lewis base adduct 2 is monomeric, but 3 exists as a novel cyclic 2.9 nm hexamer in the solid state even though it was recrystallized from the strong donor solvent THF. The reaction of H C(PPhNDipp) (Dipp = 2,6-diisopropylphenyl) with [Na(Bn)] afforded [Na{HC(PPhNDipp)}(THF)] (4). The potassium congener [K{HC(PPhNDipp)}(THF)] (5) was prepared by the reaction of the parent methane with KH. In 5, the methanide ligand is bound to potassium through one N center, the methanide center, and an η-Dipp interaction. However, the THF molecules in 5 are loosely bound, as evidenced by the isolation of dimeric [{K[HC(PPh NDipp)](THF)}] (6) from hexane. In 6, the potassium is bound to the two N centers of one methanide ligand, but no methanide-potassium interaction is observed, and a "loose" dimer is constructed by bridging K•••C interactions. The reaction of [MOR] (M = Rb, Cs) with [Li{HC(PPhNDipp)}] gave the heavy group 1 methanides [M{HC(PPhNDipp) }(THF)] [M = Rb (7), Cs (8)]. The synthetic utility of these group 1 transfer agents has been demonstrated by the preparation of [Ln{HC(PPhNMes)}(I)(THF)] [Ln = Ce (9), Pr (10), Nd (11), Sm (12)] from [Ln(I)(THF)], employing a salt metathesis methodology. Complexes 1-12 have been characterized by X-ray crystallography, multielement NMR spectroscopy, FTIR spectroscopy, and CHN microanalyses. © 2011 American Chemical Society.

Bibliographic Details

Ashley J. Wooles; Matthew Gregson; Sarah Robinson; Oliver J. Cooper; David P. Mills; William Lewis; Alexander J. Blake; Stephen T. Liddle

American Chemical Society (ACS)

Chemistry

Provide Feedback

Have ideas for a new metric? Would you like to see something else here?Let us know