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• W2029779610 abstract "The cyclooctene complex Ir(acac)(cyclooctene)(PCy 3 ) ( 1 ) reacts with methyl vinyl ketone to give Ir(acac){ η 2 -CH 2 CHC(O)CH 3 }(PCy 3 ) ( 2 ) and cyclooctene. In benzene at 70°C, complex 2 affords by means of an intramolecular CH activation process the thermodynamically favored alkenyl derivative I r(acac)H{(Z)-CHCHC(O )CH 3 }(PCy 3 ) ( 3 ), which was isolated as a mixture of the isomers 3a (PCy 3 trans to carbonyl group of alkenyl ligand) and 3b (PCy 3 trans to acac). Isomers 3a and 3b do not react with tricyclohexylphosphine. However, the complex Ir(acac)H{( E )-CHCHC(O)CH 3 }(PCy 3 ) 2 ( 4 ) can be obtained by treatment of 2 with the phosphine in benzene at 70°C. Complex 2 also reacts with HBF 4 at -78°C, to give the five-coordinate hydrido derivative [Ir(acac)H{ η 2 -CH 2 CHC(O)CH 3 }(PCy 3 )]BF 4 ( 5 ). In solution, complex 5 is only stable at temperatures lower than −40°C. At room temperature and in the presence of acetonitrile, it evolves into the alkyl compound [I r(acac){CH 2 CH 2 C(O )CH 3 }(NCCH 3 )(PCy 3 )]BF 4 ( 6 ), as a result from the selective anti -Markovnikov insertion of the carboncarbon bond of the activated olefin into the IrH bond of the 5 ." @default.
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• W2029779610 title "CH activation of methyl vinyl ketone in Ir(acac){η2-CH2CHC(O)CH3}(PCy3)" @default.
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