Ligand-controlled formation of a low-valent pincer rhodium(I)-dioxygen adduct bearing a very short O-O bond

Christian M. Frech, Linda J W Shimon, David Milstein

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Abstract

Treatment of [{Me2C6H(CH2P tBu2)2}Rh(η1-N2)] (1a) with molecular oxygen (O2) resulted in almost quantitative formation of the dioxygen adduct [{Me2C6H(CH 2PtBu2)2}Rh(η2-O 2)] (2a). An X-ray diffraction study of 2a revealed the shortest O-O bond reported for Rh-O2 complexes, indicating the formation of a RhI-O2 adduct, rather than a cyclic RhIII η2-peroxo complex. The coordination of the O2 ligand in 2a was shown to be reversible. Treatment of 2a with CO gas yielded almost quantitatively the corresponding carbonyl complex [{Me2C 6H(CH2PtBu2)2}Rh(CO)] (3a). Surprisingly, treatment of the structurally very similar pincer complex [{C6H3(CH2PiPr2) 2)}Rh(η1-N2)] (1b) with O2 led to partial decomposition, with no dioxygen adduct being observed.

Original languageEnglish
Pages (from-to)1730-1739
Number of pages10
JournalHelvetica Chimica Acta
Volume89
Issue number8
DOIs
Publication statusPublished - 2006

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Bearings (structural)
Rhodium
Molecular oxygen
Carbon Monoxide
rhodium
adducts
Ligands
Oxygen
Decomposition
X ray diffraction
ligands
Gases
X-Ray Diffraction
methylidyne
decomposition
oxygen
diffraction
gases
x rays

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Ligand-controlled formation of a low-valent pincer rhodium(I)-dioxygen adduct bearing a very short O-O bond. / Frech, Christian M.; Shimon, Linda J W; Milstein, David.

In: Helvetica Chimica Acta, Vol. 89, No. 8, 2006, p. 1730-1739.

Research output: Contribution to journalArticle

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AB - Treatment of [{Me2C6H(CH2P tBu2)2}Rh(η1-N2)] (1a) with molecular oxygen (O2) resulted in almost quantitative formation of the dioxygen adduct [{Me2C6H(CH 2PtBu2)2}Rh(η2-O 2)] (2a). An X-ray diffraction study of 2a revealed the shortest O-O bond reported for Rh-O2 complexes, indicating the formation of a RhI-O2 adduct, rather than a cyclic RhIII η2-peroxo complex. The coordination of the O2 ligand in 2a was shown to be reversible. Treatment of 2a with CO gas yielded almost quantitatively the corresponding carbonyl complex [{Me2C 6H(CH2PtBu2)2}Rh(CO)] (3a). Surprisingly, treatment of the structurally very similar pincer complex [{C6H3(CH2PiPr2) 2)}Rh(η1-N2)] (1b) with O2 led to partial decomposition, with no dioxygen adduct being observed.

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