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Dioxygenation of Sterically Hindered (Ethene)Rh I and ‐Ir I Complexes to (Peroxo)Rh III and (Ethene)(peroxo)Ir III Complexes
Author(s) -
de Bruin Bas,
Peters Theo P. J.,
Wilting Jos B. M.,
Thewissen Simone,
Smits Jan M. M.,
Gal Anton W.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200210)2002:10<2671::aid-ejic2671>3.0.co;2-8
Subject(s) - chemistry , iridium , rhodium , amine gas treating , medicinal chemistry , acetonitrile , cationic polymerization , dissociation (chemistry) , ethylene , steric effects , photochemistry , stereochemistry , polymer chemistry , catalysis , organic chemistry
New cationic, five‐coordinate bis(ethene)iridium( I ) complexes [(κ 3 ‐Me 3 ‐tpa)Ir I (ethene) 2 ] + ( 12 + ) and [(κ 3 ‐Me 2 ‐dpa‐Me)Ir I (ethene) 2 ] + ( 13 + ) have been prepared {Me 3 ‐tpa = N , N , N ‐tris[(6‐methyl‐2‐pyridyl)methyl]amine, Me 2 ‐dpa‐Me = N ‐methyl‐ N , N ‐bis[(6‐methyl‐2‐pyridyl)methyl]amine}. Complexes 12 + and 13 + lose one ethene fragment in solution, yielding the five‐coordinate mono(ethene) complex [(κ 4 ‐Me 3 ‐tpa)Ir I (ethene)] + ( 14 + ) and the four‐coordinate mono(ethene) complex [(κ 3 ‐Me 2 ‐dpa‐Me)Ir I (ethene)] + ( 15 + ), respectively. [(κ 4 ‐Me 3 ‐tpa)Rh I (ethene)] + ( 11 + ), the rhodium analogue of 14 + , was also prepared. Whereas rhodium complex 11 + is stable in acetonitrile at room temperature, the iridium analogue 14 + converts to the cyclometallated (acetonitrile)(hydrido) complex 16 + within 72 h by dissociation of the unique 6‐methylpyridyl fragment and oxidative addition of the 6‐methylpyridyl C 3 −H bond. The four‐coordinate mono(ethene) complex 15 + is even less stable in solution; it converts to a mixture of compounds within 18 h. Reaction of the mono(ethene)Rh I complex 11 + with O 2 yields the peroxo complex 17 + by ethene displacement. In contrast, the mono(ethene)Ir I complexes 14 + and 15 + bind O 2 without the loss of ethene, leading to unprecedented (ethene)(peroxo)Ir III complexes 18 + and 19 + . At room temperature, peroxo complex 17 + does not react with ethene and, quite remarkably, C−O bond formation does not occur in the (ethene)(peroxo) complexes 18 + and 19 + . (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)