C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(η1:η2-CH2CR2CH=CH 2)(CO)(PPh3)2 and trans-M(CH=CHCMeR 2)(CO)(PPh3)2 (M = Rh, Ir, R = CH 2CH2Ph)

Masumi Itazaki; Chikako Yoda; Yasushi Nishihara; Kohtaro Osakada

doi:10.1021/om049632a

C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(η¹:η²-CH₂CR₂CH=CH ₂)(CO)(PPh₃)₂ and trans-M(CH=CHCMeR ₂)(CO)(PPh₃)₂ (M = Rh, Ir, R = CH ₂CH₂Ph)

Masumi Itazaki, Chikako Yoda, Yasushi Nishihara, Kohtaro Osakada

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

Abstract

2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh ₃)₃ at room temperature and with IrH(CO)(PPh ₃)₃ at 70°C to form the 3-butenyl complexes of these metals, M{η¹:η²-CH₂C(CH ₂CH₂Ph)₂CH=CH₂}(CO)(PPh ₃)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)(PPh ₃)₃ at 115°C afford the alkenyl complexes trans-Rh{(Z)-CH=CHC(CH₂CH₂Ph)₂CH ₃}-(CO)(PPh₃)₂ (3) and trans-Ir{(E)-CH= CHC(CH₂CH₂Ph)₂CH₃}(CO)(PPh ₃)₂ (4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HC≡CC(CH₂CH₂Ph)₂CH ₃ reacts with MH(CO)(PPh₃)₃ (M = Rh, Ir) to afford the alkynyl complexes trans-M{C≡CC(CH₂CH ₂Ph)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.

Original language	English
Pages (from-to)	5402-5409
Number of pages	8
Journal	Organometallics
Volume	23
Issue number	23
DOIs	https://doi.org/10.1021/om049632a
Publication status	Published - Nov 8 2004
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(η¹:η²-CH₂CR₂CH=CH ₂)(CO)(PPh₃)₂ and trans-M(CH=CHCMeR ₂)(CO)(PPh₃)₂ (M = Rh, Ir, R = CH ₂CH₂Ph). / Itazaki, Masumi; Yoda, Chikako; Nishihara, Yasushi et al.
In: Organometallics, Vol. 23, No. 23, 08.11.2004, p. 5402-5409.

Research output: Contribution to journal › Article › peer-review

Itazaki, M, Yoda, C, Nishihara, Y & Osakada, K 2004, 'C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(η¹:η²-CH₂CR₂CH=CH ₂)(CO)(PPh₃)₂ and trans-M(CH=CHCMeR ₂)(CO)(PPh₃)₂ (M = Rh, Ir, R = CH ₂CH₂Ph)', Organometallics, vol. 23, no. 23, pp. 5402-5409. https://doi.org/10.1021/om049632a

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title = "C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(η1:η2-CH2CR2CH=CH 2)(CO)(PPh3)2 and trans-M(CH=CHCMeR 2)(CO)(PPh3)2 (M = Rh, Ir, R = CH 2CH2Ph)",

abstract = "2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh 3)3 at room temperature and with IrH(CO)(PPh 3)3 at 70°C to form the 3-butenyl complexes of these metals, M{η1:η2-CH2C(CH 2CH2Ph)2CH=CH2}(CO)(PPh 3)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)(PPh 3)3 at 115°C afford the alkenyl complexes trans-Rh{(Z)-CH=CHC(CH2CH2Ph)2CH 3}-(CO)(PPh3)2 (3) and trans-Ir{(E)-CH= CHC(CH2CH2Ph)2CH3}(CO)(PPh 3)2 (4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HC≡CC(CH2CH2Ph)2CH 3 reacts with MH(CO)(PPh3)3 (M = Rh, Ir) to afford the alkynyl complexes trans-M{C≡CC(CH2CH 2Ph)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.",

author = "Masumi Itazaki and Chikako Yoda and Yasushi Nishihara and Kohtaro Osakada",

year = "2004",

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T1 - C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(η1:η2-CH2CR2CH=CH 2)(CO)(PPh3)2 and trans-M(CH=CHCMeR 2)(CO)(PPh3)2 (M = Rh, Ir, R = CH 2CH2Ph)

AU - Itazaki, Masumi

AU - Yoda, Chikako

AU - Nishihara, Yasushi

AU - Osakada, Kohtaro

PY - 2004/11/8

Y1 - 2004/11/8

N2 - 2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh 3)3 at room temperature and with IrH(CO)(PPh 3)3 at 70°C to form the 3-butenyl complexes of these metals, M{η1:η2-CH2C(CH 2CH2Ph)2CH=CH2}(CO)(PPh 3)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)(PPh 3)3 at 115°C afford the alkenyl complexes trans-Rh{(Z)-CH=CHC(CH2CH2Ph)2CH 3}-(CO)(PPh3)2 (3) and trans-Ir{(E)-CH= CHC(CH2CH2Ph)2CH3}(CO)(PPh 3)2 (4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HC≡CC(CH2CH2Ph)2CH 3 reacts with MH(CO)(PPh3)3 (M = Rh, Ir) to afford the alkynyl complexes trans-M{C≡CC(CH2CH 2Ph)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.

AB - 2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh 3)3 at room temperature and with IrH(CO)(PPh 3)3 at 70°C to form the 3-butenyl complexes of these metals, M{η1:η2-CH2C(CH 2CH2Ph)2CH=CH2}(CO)(PPh 3)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)(PPh 3)3 at 115°C afford the alkenyl complexes trans-Rh{(Z)-CH=CHC(CH2CH2Ph)2CH 3}-(CO)(PPh3)2 (3) and trans-Ir{(E)-CH= CHC(CH2CH2Ph)2CH3}(CO)(PPh 3)2 (4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HC≡CC(CH2CH2Ph)2CH 3 reacts with MH(CO)(PPh3)3 (M = Rh, Ir) to afford the alkynyl complexes trans-M{C≡CC(CH2CH 2Ph)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.

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