Journal of Organometallic Chemistry p. 39 - 54 (1998)
Update date:2022-08-05
Topics:
Chen, Ai-Jan
Su, Chung-Chi
Tsai, Fu-Yu
Lee, Jen-Jeh
Huang, Tsang-Miao
Yang, Ching-Shuenn
Lee, Gene-Hsiang
Wang, Yu
Chen, Jwu-Ting
Regioselective addition of ammonia, primary or secondary amines, aniline, or amino derivatives either to a neutral (η1-allenyl)platinum complex trans-Pt(Br)(PPh3)2(η1-CHCCH2) (1) or to a cationic η3-allenyl/propargyl platinum complex [Pt(PPh3)2(η3-C3H 3)](BF4) (2) provide the synthesis of cationic N-protonated, N-alkylated, and N-arylated η3-azatrimethylenemethane complexes {Pt(PPh3)2(η3-CH 2C(NRR′)CH2]}(X) (R=H R′=H (3a), Me (3b), Et (3c), iPr (3d), tBu (3e), c-C6H11 (3f), Ph (3g), CH2CH2OH (3h), R=R′=Et (3i), c-C3H6 (from azetidine 3j), Ph (3k), R=Me R′=Ph (3l); X=Br, BF4), respectively. Addition of amides to 1 gave a neutral η3-azatrimethylenemethane complex Pt(PPh3)2[η3-CH2C(NSO 2Ph)CH2] (4m). Similar reactions using palladium complexes yield {Pd(PPh3)2[η3-CH 2C(NRR′)CH2]}(X) (R=H R′=iPr (7d), Ph (7g), R=R′=Et (7i); X=Br, BF4, OTf), Pd(Br)(PPh3)[η3-CH2C(NEt 2)CH2] (8i) and Pd(PPh3)2[η3-CH2C(NR)CH 2] (R=SO2Ph (9m), p-SO2C6H4Me (9n)). Synthesis of three complexes, {M(PPh3)2[η3-CH2C(NHR)CH 2]}+ (M=Pt R=SO2Ph (3m); M=Pd R=SO2Ph (7m), p-SO2C6H4Me (7n)), can not be done by hydroamination reactions, but has been successful using protonation of η3-N-TMM complexes 4m, 9m, and 9n, respectively. Spectroscopic and crystallographic characterizations indicate that these N-TMM complexes exhibit intermediary structural features between η3-2-aminoallyl and metallacyclobutanimine complexes.We designate η3-O-TMM to stand for the η3-oxatrimethylenemethane complexes M[η3-CH2C(=O)CH2]; η3-N-TMM to stand for the η3-azatrimethylenemethane complexes M[η3-CH2C(=NR)CH2]. Accordingly, N-protonated η3-N-TMM complexes are referred to M[η3-CH2C(NH2)CH2]; and N-alkylated or N-arylated η3-N-TMM complexes are referred to M[η3-CH2C(NHR)CH2] or M[η3-CH2C(NRR′)CH2] (R, R′=alkyl or aryl).
View MoreSHANGHAI T&W PHARMACEUTICAL CO., LTD.
website:http://www.trustwe.com
Contact:+86-21-61551611
Address:601, No. 1, 2277 Nong, Zu Chongzhi Road, Zhangjiang Hightech. Park, Pudong
website:http://www.sjzthld.com
Contact:86-311-66699812
Address:NO.600 ZHONGSHAN EAST ROAD SHIJIAZHUANG
Contact:0510-85393305
Address:1619 Huishan Avenue, Huishan District, Wuxi,
NingBO Hong Xiang Biochem.Co.Ltd
website:http://www.hxbiochem.com
Contact:0574-66003444
Address:Ning Bo Bei Lun
Chengdu Boon Stream Chemical Industry Co.,Ltd.
Contact:+86-28-83156758
Address:No.859,Dongzikou Road,Jinniu District,Chengdu,Sichuan,P.R.China
Doi:10.1080/00397919908086455
(1999)Doi:10.1021/ol990761a
(1999)Doi:10.1039/j39700002266
(1970)Doi:10.1016/0040-4039(90)87038-2
(1990)Doi:10.1016/S0040-4039(99)00930-2
(1999)Doi:10.1021/om9810347
(1999)