Synthesis and reactivity of a transition metal complex containing exclusively TEMPO ligands

Ni(η2-TEMPO)2

Derek Isrow, Burjor Captain

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The reaction of Ni(COD)2 with two equivalents of the TEMPO radical at 68 °C affords the 16 e- "bow-tie" complex Ni(η2-TEMPO)2, 1, in 78% yield. Compound 1 reacts with tert-butyl isocyanide and phenylacetylene at room temperature to yield the 16 e- distorted square planar nickel complexes Ni(η2- TEMPO)(η1-TEMPO)(CNtBu), 2, and Ni(η2- TEMPO)(η1-TEMPOH)(CCPh), 4, respectively. The facile reactivity of 1 is aided by the transition of the TEMPO ligand from an η2 to η1 binding mode. Complex 4 is an unusual example of hydrogen atom transfer from phenylacetylene to a coordinated TEMPO ligand.

Original languageEnglish
Pages (from-to)5864-5866
Number of pages3
JournalInorganic Chemistry
Volume50
Issue number13
DOIs
StatePublished - Jul 4 2011

Fingerprint

Coordination Complexes
Transition metals
reactivity
transition metals
Ligands
ligands
crack opening displacement
bows
synthesis
hydrogen atoms
nickel
Nickel
Hydrogen
room temperature
Atoms
2,2,4,4-tetramethylpiperdine-1-oxyl
TEMPO
Temperature
phenylacetylene

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Synthesis and reactivity of a transition metal complex containing exclusively TEMPO ligands : Ni(η2-TEMPO)2. / Isrow, Derek; Captain, Burjor.

In: Inorganic Chemistry, Vol. 50, No. 13, 04.07.2011, p. 5864-5866.

Research output: Contribution to journalArticle

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AB - The reaction of Ni(COD)2 with two equivalents of the TEMPO radical at 68 °C affords the 16 e- "bow-tie" complex Ni(η2-TEMPO)2, 1, in 78% yield. Compound 1 reacts with tert-butyl isocyanide and phenylacetylene at room temperature to yield the 16 e- distorted square planar nickel complexes Ni(η2- TEMPO)(η1-TEMPO)(CNtBu), 2, and Ni(η2- TEMPO)(η1-TEMPOH)(CCPh), 4, respectively. The facile reactivity of 1 is aided by the transition of the TEMPO ligand from an η2 to η1 binding mode. Complex 4 is an unusual example of hydrogen atom transfer from phenylacetylene to a coordinated TEMPO ligand.

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