A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

Journal of Chemical Sciences

Joel T Mague²  Guddekoppa S Ananthnag¹  Maravanji S Balakrishna1¹ 

[1] Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India$$;Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA$$

关键词: Cyclodiphosphazanes;    cis/trans isomerisation;    NMR studies;    complexes;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

The hydrolysis of cis-{ClP(𝜇-N𝑡Bu)2P(NH𝑡Bu)} (1) produced a mixed PIII/PV derivative of cyclodiphosphazane, cis-{(𝑡BuNH)P(𝜇-N𝑡Bu)2P(O)H} (2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-{(𝑡BuNH)P(Se)(𝜇-N𝑡Bu)2P(O)H} (3) in good yield. The reactions of two equivalent of 2 with [Pd(𝜇-Cl)(𝜂3-C3H5)]2 or [Ru(𝜂6-𝑝-cymene)(𝜇-Cl)Cl]2 in dichloromethane afforded corresponding mononuclear complexes, [(𝜂3-C3H5)PdCl{(𝑡BuNH)P(𝜇-N𝑡Bu)2P(O)H}] (4) and [((𝜂6-𝑝-cymene)RuCl2){(𝑡BuNH)P(𝜇-N𝑡Bu)2P(O)H}] (5). The treatment of 2 with M(COD)Cl2 (M = Pd and Pt) in dichloromethane at room temperature gave [MCl2{(𝑡BuNH)P(𝜇-N𝑡Bu)2P(O)H}2] (6 M = Pd; 7 M = Pt) in good yield. Owing to the cis/trans isomerisation of the cyclodiphosphazane rings, the complexes 6 and 7 exist as a mixture of two isomers. Various NMR spectroscopic techniques were employed for structural elucidation. The molecular structures of 5 and 7 were established by single crystal X-ray crystallographic studies.

【 授权许可】

Unknown