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 language | English |
|---|---|
| Pages (from-to) | 1730-1739 |
| Number of pages | 10 |
| Journal | Helvetica Chimica Acta |
| Volume | 89 |
| Issue number | 8 |
| DOIs | |
| Publication status | Published - 2006 |
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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 journal › Article
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TY - JOUR
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
Y1 - 2006
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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U2 - 10.1002/hlca.200690170
DO - 10.1002/hlca.200690170
M3 - Article
AN - SCOPUS:33748444788
VL - 89
SP - 1730
EP - 1739
JO - Helvetica Chimica Acta
JF - Helvetica Chimica Acta
SN - 0018-019X
IS - 8
ER -