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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Published on: April 10, 2015

Exocyclic bond cleavage in oxaphosphirane complexes?

Arturo Espinosa1, Rainer Streubel

  • 1Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain. artuesp@um.es

Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 7, 2012
PubMed
Summary

This study computationally investigates exocyclic bonds in phosphorus-containing metal complexes. Heterolytic cleavage is favored, especially with bulky substituents, and SET reactions offer pathways for decomplexation and P-functionalization.

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Area of Science:

  • Organometallic Chemistry
  • Computational Chemistry
  • Phosphorus Chemistry

Background:

  • Oxaphosphirane complexes featuring exocyclic bonds to phosphorus are of interest.
  • Understanding the intrinsic strength and cleavage pathways of these bonds is crucial for synthetic applications.

Purpose of the Study:

  • To computationally investigate the intrinsic strength of exocyclic P-R bonds in oxaphosphirane κP-pentacarbonylmetal(0) complexes.
  • To analyze the reactivity of these complexes towards single electron transfer (SET) reactions.
  • To provide insights for designing synthetic strategies for decomplexation and P-functionalization.

Main Methods:

  • Computational analysis of bond cleavage energies (homolytic vs. heterolytic).
  • Application of the facile variation of bond-strength-related descriptors (VBSD) methodology.
  • Evaluation of reactivity towards oxidative and reductive single electron transfer (SET).

Main Results:

  • Heterolytic cleavage of the P-R bond is the lowest-energy pathway, particularly for bulky R groups like trityl.
  • P-M bond cleavage requires approximately 30 kcal mol(-1) and decreases with increasing R bulk and from Cr to Mo.
  • Reductive SET reactions allow selective P-M cleavage for P-Me and P-tBu, while P-R cleavage is favored for P-trityl complexes.

Conclusions:

  • The study provides the first computational insight into the intrinsic strength of exocyclic bonds to phosphorus in these complexes.
  • SET reactions offer tunable pathways for selective bond cleavage, enabling decomplexation or P-functionalization.
  • The anionic oxaphosphiranide complex is identified as a potential key intermediate for further synthetic modifications.