Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes
The present work describes the design and synthesis of a series of rhodium and iridium dimers [(η5-ring)MCl]2(μ2-Cl)2 (where (η5-ring)MCl = (η5-Me4C5R)Rh(III)Cl or (η
Brown, Loren C.,Ressegue, Emily,Merola, Joseph S.
p. 4014 - 4022
(2017/01/09)
Extending the range of pentasubstituted cyclopentadienyl compounds: The synthesis of a series of tetramethyl(alkyl or aryl)cyclopentadienes (Cp?R), their iridium complexes and their catalytic activity for asymmetric transfer hydrogen
Tetramethyl(alky or aryl)cyclopentadienes were synthesized and the organometallic half-sandwich iridium complexes of the form [(η5-Cp?R)Ir(aa)Cl], Cp?R = tetramethyl(phenyl)cyclopentadienyl (Cp?
Morris, David M.,McGeagh, Michael,De Pe?a, David,Merola, Joseph S.
p. 120 - 135
(2015/02/19)
Relative Importance of Dissociative Loss of Carbon Monoxide and Formation of Benzyl Radicals from Photoexcitation of (η5-C5R5)Fe(CO)2(η1-CH2C6H5) and Evidence for Reaction of Carbon Monoxide with 17-Electron Radicals
Near-UV irradiation of (η5-C5R5)Fe(CO)2(η1-CH2C6H5) (R=H, Me) yields both loss of CO and CH2C6H5 radicals as primary photoprocesses, though the loss of CO dominates the excited-state chemistry.At 77 K in a rigid alkane matrix the only detectable photoreaction is loss of CO to form (η5-C5R5)Fe(CO)(η3-CH2C6H5).In fluid alkane solution at 298 K the dominant metal-containing photoproduct is (η5-C5R5)2Fe2(CO)4, unless the solution is actively purged with a stream of an inert gas such as Ar or N2.When the solution is purged with Ar there are two main products: (η5-C5R5)Fe(CO)(η3-CH2C6H5) (90-95percent) and (η5-C5R5)2Fe2(CO)4 (5-10percent).The 366-nm quantum efficiency for CO loss is ca. 0.5, and that for CH2C6H5 loss is ca. 0.05.When (η5-C5R5)Fe(CO)2(η1-CH2C6H5) is irradiated under 2 atm of CO in alkane solution at 298 K (η4-C5R5(CH2C6H5))Fe(CO)3 is formed in good chemical yield (>50percent).X-ray crystallography establishes (η4-C5Me5(CH2C6H5))Fe(CO)3 to have the CH2C6H5 group in an exo position.The formation of (η4-C5R5(CH2C6H5))Fe(CO)3 occurs via light-induced loss of a CH2C6H5 radical from (η5-C5R5)Fe(CO)2(η1-CH2C6H5) followed by reaction of (η5-C5R5)Fe(CO)2 with CO to form (C5R5)Fe(CO)3 that then couples with a CH2C6H5 radical to give the exo isomer of (η4-C5R5(CH2C6H5))Fe(CO)3.
Blaha, Josephine Paw,Wrighton, Mark S.
p. 2694 - 2702
(2007/10/02)
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