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Terminal imido rhodium complexes.

Ana M Geer1, Cristina Tejel, José A López

  • 1Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain).

Angewandte Chemie (International Ed. in English)
|April 15, 2014
PubMed
Summary
This summary is machine-generated.

Researchers synthesized the first terminal imido rhodium complexes, featuring a multiple Rh=N bond. These novel compounds exhibit unique reactivity, including protonation and cycloaddition reactions, expanding organometallic chemistry.

Keywords:
azidescycloadditionmultiple bondsrhodiumstructure elucidation

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry

Background:

  • Late transition metal compounds with M=X multiple bonds are synthetically challenging.
  • Isolated examples of terminal imido complexes are scarce, especially for second- and third-row elements.

Purpose of the Study:

  • To synthesize and characterize the first terminal imido rhodium complexes.
  • To investigate the reactivity of the novel Rh=N bond.

Main Methods:

  • Reaction of organic azides with a rhodium(I) precursor.
  • Isolation and characterization using spectroscopic and crystallographic techniques.
  • Preliminary reactivity studies including protonation, hydrogenation, and cycloaddition.

Main Results:

  • Isolation of the first rhodium complexes with a terminal Rh=N multiple bond, [Rh(PhBP3)(NR)].
  • Characterization revealed a pseudo-tetrahedral geometry and a short Rh-N bond (1.780(2) Å).
  • The Rh=N bond undergoes protonation, H2 addition, nitrene-group transfer, and cycloaddition reactions.

Conclusions:

  • Successful synthesis and characterization of unprecedented terminal imido rhodium complexes.
  • Demonstration of diverse reactivity associated with the Rh=N multiple bond.
  • Opens new avenues for exploring late transition metal imido chemistry.