215608-55-2Relevant academic research and scientific papers
A new stable intermediary mode between η3-2-aminoallyl complexes and metallacyclobutanimines. Synthesis and structural characteristic of η3-azatrimethylenemethane and N-protonated, N-alkylated, N-arylated η3-azatrimethylenemethane complexes of Pt and Pd
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
, p. 39 - 54 (2007/10/03)
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).
