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Related Experiment Videos

[Me3SiN(PPh3)-ICN]: a new labile donor-acceptor complex.

R Kempe1, E Kessenich, A Schulz

  • 1The Max Planck Institute of Rostock, Germany.

Inorganic Chemistry
|September 18, 2001
PubMed
Summary
This summary is machine-generated.

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Trimethylsilyl phosphanimine reacts with pseudohalogens. The intermediate adduct with iodine cyanide (ICN) is metastable, forming a labile donor-acceptor complex with weak N-I bonds.

Area of Science:

  • Organosilicon chemistry
  • Pseudohalogen reactivity
  • Coordination chemistry

Background:

  • Trimethylsilyl phosphanimine (Me3SiNPPh3) is a key reagent in organosilicon and phosphorus chemistry.
  • Pseudohalogens (XCN) are versatile synthons with diverse reactivity.
  • Understanding adduct formation is crucial for controlling reaction pathways.

Purpose of the Study:

  • To investigate the reaction of Me3SiNPPh3 with pseudohalogens XCN (X = Cl, Br, I).
  • To characterize the intermediate adduct complexes formed.
  • To elucidate the structure and bonding of the metastable adduct.

Main Methods:

  • Solution-phase reaction studies.
  • Isolation and characterization of adducts.
  • Raman spectroscopy and X-ray diffraction analysis.

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  • Natural bond orbital (NBO) and valence bond (VB) calculations.

    • Main Results:

    • Me3SiNPPh3 forms adducts with XCN species.
    • Only the iodine cyanide (ICN) adduct, [Me3SiN(PPh3)-ICN], is metastable.
    • The ICN adduct decomposes into Ph3PNCN and Me3SiX.
    • Raman and X-ray data reveal a labile donor-acceptor complex with two long N...I bonds (2.634(1) and 2.739(14) Å).

    Conclusions:

    • The reaction of Me3SiNPPh3 with ICN yields a transient, weakly bound adduct.
    • The N-I bond in the adduct is highly labile, facilitating further decomposition.
    • Computational analyses support the weak donor-acceptor interaction and bonding characteristics.