Source:http://linkedlifedata.com/resource/pubmed/id/18594702
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
27
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pubmed:dateCreated |
2008-7-2
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pubmed:abstractText |
Reaction of [Cp*Ir(micro-H)](2) (5) (Cp* = eta(5)-C(5)Me(5)) with bis(dimethylphosphino)methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir)(2)(micro-dmpm)(micro-H)(2)] (3). Treatment of 3 with methyl triflate at -30 degrees C results in the formation of [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Me)(IrCp*)][OTf] (6). Warming a solution of above 0 degrees C brings about predominant generation of 32e(-) Ir(II)-Ir(II) species [(Cp*Ir)(micro-dmpm)(micro-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 degrees C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(micro-Me(2)PCH(2)PMeCH(2))(micro-H)(IrCp*)][OTf] (8), which is formed by intramolecular oxidative addition of the methyl C-H bond of the dmpm ligand. Intermolecular C-H bond activation reactions with 7 are also examined. Reactions of 7 with aromatic molecules (benzene, toluene, furan, and pyridine) at room temperature result in the smooth sp(2) C-H activation to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H)(micro-dmpm)(micro-C(5)H(4)N)(H)(IrCp*)][OTf] (12), respectively. Complex also reacts with cyclopentene at 0 degrees C to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis.
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pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical |
http://linkedlifedata.com/resource/pubmed/chemical/Carbon,
http://linkedlifedata.com/resource/pubmed/chemical/Hydrogen,
http://linkedlifedata.com/resource/pubmed/chemical/Iridium,
http://linkedlifedata.com/resource/pubmed/chemical/Ligands,
http://linkedlifedata.com/resource/pubmed/chemical/Mesylates,
http://linkedlifedata.com/resource/pubmed/chemical/Organometallic Compounds,
http://linkedlifedata.com/resource/pubmed/chemical/Phosphines,
http://linkedlifedata.com/resource/pubmed/chemical/methyl triflate
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pubmed:status |
MEDLINE
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pubmed:month |
Jul
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pubmed:issn |
1477-9226
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pubmed:author | |
pubmed:issnType |
Print
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pubmed:day |
21
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
3546-52
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pubmed:meshHeading | |
pubmed:year |
2008
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pubmed:articleTitle |
C-H activation on a diphosphine and hydrido-bridged diiridium complex: generation and detection of an active IrII-IrII species [(Cp*Ir)2(micro-dmpm)(micro-H)]+.
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pubmed:affiliation |
Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan. yama@kagaku.mbox.media.kyoto-u.ac.jp.
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pubmed:publicationType |
Journal Article,
Research Support, Non-U.S. Gov't
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