The reaction of cis-[PtCl2(dmso)2] with ligands 4-ClC6H4CHNCH2C6H5 (1a) and 4-ClC6H4CHNCH2(4-ClC6H4) (1b) in the presence of sodium acetate and using either methanol or toluene as solvent produced the corresponding five-membered endo-metallacycles [PtCl(4-ClC6H3)CHNCH2C6H5}SOMe2}] (2a) and [PtCl(4-ClC6H3)CHNCH2(4′-ClC6H4)}SOMe2}] (2b). An analogous reaction for ligands 2,6-Cl2C6H3CHNCH2C6H5 (1c) and 2,6-Cl2C6H3CHNCH2(4-ClC6H4) (1d) produced five-membered exo-metallacycles [PtCl(2,6-Cl2C6H3)CHNCH2C6H4}SOMe2}] (2c) and [PtCl(2,6-Cl2C6H3)CHNCH2(4′-ClC6H3)}SOMe2}] (2d) when the reaction was carried out in methanol and seven-membered endo-platinacycles [PtCl(MeC6H3)ClC6H3CHNCH2C6H4}SOMe2}] (3c) and [PtCl(MeC6H3)ClC6H3CHNCH2(4′-ClC6H3)}SOMe2}] (3d) when toluene was used as a solvent. The reaction of 2,4,6-(CH3)3C6H2CHNCH2(4-ClC6H4) (1e) produced in both solvents an exo-platinacycle [PtCl(2,4,6-(CH3)3C6H2)CHNCH2(4′-ClC6H3)}SO(CH3)2}] (2e). Cyclometallation of 4-chlorobenzylamine was also achieved to produce compound [PtCl(4-ClC6H3)CH2NH2}SOMe2}] (2g). The reactions of endo- and exo-metallacycles with phosphines evidenced the higher lability of the Pt–N bond in exo-metallacycles while a comparative analysis of the crystal structures points out a certain degree of aromaticity in the endo-metallacycle.
6-
CH3)3C6H2CHNCH2(4-ClC6H4)}SOMe2}] (2e)和[PtCl(2,4,6- )3C6H2CHNCH2(4′-ClC6H3)}Scis-[PtCl2(dmso)2]与
配体4-ClC6H4CHNCH2C6H5 (1a)和4-ClC6H4CHNCH2(4-ClC6H4) (1b)在
乙酸钠存在下发生反应,使用
甲醇或
甲苯作为溶剂,生成相应的五元内型
金属环[PtCl(4-ClC6H3)CHNCH2C6H5}SOMe2}] (2a)和[PtCl(4-ClC6H3)CHNCH2(4′-ClC6H4)}SOMe2}] (2b)。
配体2,6-Cl2C6H3CHNCH2C6H5 (1c)和2,6-Cl2C6H3CHNCH2(4-ClC6H4) (1d)发生类似反应,在
甲醇中反应生成五元外型
金属环[PtCl(2,6-Cl2C6H3)CHNCH