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Ligand‐Controlled Formation of a Low‐Valent Pincer Rhodium(I)–Dioxygen Adduct Bearing a Very Short OO Bond
Author(s) -
Frech Christian M.,
Shimon Linda J. W.,
Milstein David
Publication year - 2006
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200690170
Subject(s) - chemistry , adduct , rhodium , pincer movement , ligand (biochemistry) , transition metal dioxygen complex , pincer ligand , stereochemistry , medicinal chemistry , oxygen , catalysis , receptor , organic chemistry , biochemistry
Treatment of [{Me 2 C 6 H(CH 2 P t Bu 2 ) 2 }Rh( η 1 ‐N 2 )] ( 1a ) with molecular oxygen (O 2 ) resulted in almost quantitative formation of the dioxygen adduct [{Me 2 C 6 H(CH 2 P t Bu 2 ) 2 }Rh( η 2 ‐O 2 )] ( 2a ). An X‐ray diffraction study of 2a revealed the shortest OO bond reported for RhO 2 complexes, indicating the formation of a Rh I O 2 adduct, rather than a cyclic Rh III η 2 ‐peroxo complex. The coordination of the O 2 ligand in 2a was shown to be reversible. Treatment of 2a with CO gas yielded almost quantitatively the corresponding carbonyl complex [{Me 2 C 6 H(CH 2 P t Bu 2 ) 2 }Rh(CO)] ( 3a ). Surprisingly, treatment of the structurally very similar pincer complex [{C 6 H 3 (CH 2 P i Pr 2 ) 2 )}Rh( η 1 ‐N 2 )] ( 1b ) with O 2 led to partial decomposition, with no dioxygen adduct being observed.