Ligand‐Controlled Formation of a Low‐Valent Pincer Rhodium(I)–Dioxygen Adduct Bearing a Very Short O?O Bond |
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| Authors: | Christian&#x M. Frech,Linda&#x J.&#x W. Shimon,David Milstein |
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| Affiliation: | Christian M. Frech,Linda J. W. Shimon,David Milstein |
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| Abstract: | Treatment of [{Me2C6H(CH2PtBu2)2}Rh(η1‐N2)] ( 1a ) with molecular oxygen (O2) resulted in almost quantitative formation of the dioxygen adduct [{Me2C6H(CH2PtBu2)2}Rh(η2‐O2)] ( 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 [{Me2C6H(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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| Keywords: | Rhodium complexes Pincer Dioxygen complexes Oxygen transfer Ligand effects |
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