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

doi:10.1002/hlca.200690170

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

Weizmann Institute of Science, Israel

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

36 Citations (Scopus)

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 ₂P^tBu₂)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 Rh^I-O₂ adduct, rather than a cyclic Rh^III 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(CH₂P^tBu₂)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 language	English
Pages (from-to)	1730-1739
Number of pages	10
Journal	Helvetica Chimica Acta
Volume	89
Issue number	8
DOIs	https://doi.org/10.1002/hlca.200690170
Publication status	Published - Sep 14 2006

ASJC Scopus subject areas

Catalysis
Biochemistry
Drug Discovery
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{fc5b151a63d6409f90287d3a35a992ee,

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

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.",

author = "Frech, {Christian M.} and Shimon, {Linda J.W.} and David Milstein",

year = "2006",

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doi = "10.1002/hlca.200690170",

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T1 - Ligand-controlled formation of a low-valent pincer rhodium(I)-dioxygen adduct bearing a very short O-O bond

AU - Frech, Christian M.

AU - Shimon, Linda J.W.

AU - Milstein, David

PY - 2006/9/14

Y1 - 2006/9/14

N2 - 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.

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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JO - Helvetica Chimica Acta

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