Synthesis and reactivity of a transition metal complex containing exclusively TEMPO ligands: Ni(η2-TEMPO)2

Derek Isrow; Burjor Captain

doi:10.1021/ic2007342

Synthesis and reactivity of a transition metal complex containing exclusively TEMPO ligands: Ni(η²-TEMPO)₂

Derek Isrow, Burjor Captain

Chemistry

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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)(CN^tBu), 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 language	English (US)
Pages (from-to)	5864-5866
Number of pages	3
Journal	Inorganic Chemistry
Volume	50
Issue number	13
DOIs	https://doi.org/10.1021/ic2007342
State	Published - Jul 4 2011

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Synthesis and reactivity of a transition metal complex containing exclusively TEMPO ligands: Ni(η2-TEMPO)2",

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.",

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N2 - 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.

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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