%0 Journal Article %A Itazaki, Masumi %A Yoda, Chikako %A Nishihara, Yasushi %A Osakada, Kohtaro %D 2004 %T C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η12-CH2CR2CHCH2)(CO)(PPh3)2 and trans-M(CHCHCMeR2)(CO)(PPh3)2 (M = Rh, Ir, R = CH2CH2Ph) %U https://acs.figshare.com/articles/journal_contribution/C_C_and_C_H_Bond_Activation_of_Dialkylmethylenecyclopropane_Promoted_by_Rhodium_and_Iridium_Complexes_Preparation_and_Structures_of_M_sup_1_sup_sup_2_sup_CH_sub_2_sub_CR_sub_2_sub_CH_CH_sub_2_sub_CO_PPh_sub_3_sub_sub_2_sub_and_i_trans_i_M_CH_CHCMeR_sub_2_/3317173 %R 10.1021/om049632a.s001 %2 https://acs.figshare.com/ndownloader/files/5155906 %K reaction mechanisms %K Dialkylmethylenecyclopropane Promoted %K alkenyl complexes trans %K Heating 1 %K HC %K H 2 %K MH %K Iridium Complexes %K η 2 %K CO %K 2 CH 3 %K CR %K NMR %K η 1 %K oxidative addition %K alkynyl complexes trans %K metal center %K room temperature %K CH 2 CH 2 Ph %X 2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh3)3 at room temperature and with IrH(CO)(PPh3)3 at 70 °C to form the 3-butenyl complexes of these metals, M{η1:η2-CH2C(CH2CH2Ph)2CHCH2}(CO)(PPh3)2 (1, M = Rh; 2, M = Ir). Heating 1 at 55 °C liberates 1,1-bis(2-phenylethyl)-1,3-butadiene, while the thermal reaction of 2 at 110 °C forms a mixture of 3-methyl-3-vinyl-1,5-diphenyl-1-pentene (48% NMR yield) and 3-methyl-3-vinyl-1,5-diphenylpentane (15% NMR yield). The reactions of excess amounts of 2,2-bis(2-phenylethyl)-1-methylenecyclopropane with RhH(CO)(PPh3)3 at 55 °C and with IrH(CO)(PPh3)3 at 115 °C afford the alkenyl complexes trans-Rh{(Z)-CHCHC(CH2CH2Ph)2CH3}(CO)(PPh3)2 (3) and trans-Ir{(E)-CHCHC(CH2CH2Ph)2CH3}(CO)(PPh3)2 (4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HC⋮CC(CH2CH2Ph)2CH3 reacts with MH(CO)(PPh3)3 (M = Rh, Ir) to afford the alkynyl complexes trans-M{C⋮CC(CH2CH2Ph)2CH3}(CO)(PPh3)2 (5, M = Rh; 6, M = Ir) via oxidative addition of the C(alkyne)−H bond to the metal center and subsequent elimination of H2. %I ACS Publications